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DOI: 10.2200/S00057ED1V01Y200712ENG04
DOI: 10.2200/S00058ED1V01Y200712ENG05
Lecture #4
Series ISSN
ISSN 19395221 print
ISSN 1939523X electronic
Tensor Properties of Solids
Phenomenological Development of the
Tensor Properties of Crystals
Richard F. Tinder
Washington State University
M
&C Mor gan & Cl aypool Publishers
iv
ABSTRACT
Tensor Properties of Solids presents the phenomenological development of solid state properties rep
resented as matter tensors in two parts: Part I on equilibrium tensor properties and Part II on
transport tensor properties.
Part I begins with an introduction to tensor notation, transformations, algebra, and calcu
lus together with the matrix representations. Crystallography, as it relates to tensor properties of
crystals, completes the background treatment. A generalized treatment of solidstate equilibrium
thermodynamics leads to the systematic correlation of equilibrium tensor properties. This is fol
lowed by developments covering rst, second, third, and higherorder tensor effects. Included
are the generalized compliance and rigidity matrices for rstorder tensor properties, Maxwell rela
tions, effect of measurement conditions, and the dependent coupled effects and use of interaction
diagrams. Part I concludes with the second and higherorder effects, including numerous optical
tensor properties.
Part II presents the driving forces and uxes for the wellknown proper conductivities. An
introduction to irreversible thermodynamics includes the concepts of microscopic reversibility,
Onsagers reciprocity principle, entropy density production, and the proper choice of the transport
parameters. This is followed by the forceux equations for electronic charge and heat ow and the
relationships between the proper conductivities and phenomenological coefcients. The thermo
electric effects in solids are discussed and extended to the piezothermoelectric and piezoresistance
tensor effects. The subjects of thermomagnetic, galvanomagnetic, and thermogalvanomagnetic ef
fects are developed together with other higherorder magnetotransport property tensors.
A glossary of terms, expressions and symbols are provided at the end of the text, and end
ofchapter problems are provided on request. Endnotes provide the necessary references for further
reading.
KEYWORDS
tensor properties, crystals, thermodynamics, equilibrium, transport
v
Preface
An exhaustive indepth treatment of the tensor properties of crystals would be a daunting task and
would require several books on the subject, each of which would be of considerable length. This
would require each property, experimentally known to exist or predicted by theory, to be developed
from rst principles at the atomic or quantum mechanical level. This is not what this text is about.
We purport to develop the physical properties of solids (actually crystals) from the thermodynamic
and tensorial points of view, which, if done correctly, provide a valuable introduction to a multitude
of physical properties. The phenomenological development used in this text permits a thermody
namic basis for property denitions that is inviolate or nearly so. However, it is correct to say that
many of the matter tensor properties dened in this way may not have been studied previously to
establish their relative importance.
This text is designed to be used as a onesemester or twoquarter course in the subject matter.
It also serves as a valuable source of information for practicing engineers and scientists in related
elds. Although the text provides the necessary background in tensor analysis, the readership is
expected to have some knowledge of calculus and matrix algebra. An understanding of basic vec
tor analysis is also deemed helpful. The necessary information regarding crystallography and point
groups as they relate to this text is provided as background material in the text.
The contents of this text are based on the authors notes used for a graduate course taught
over several years at Washington State University to graduate students and secondsemester seniors
in the areas of material science, electrical and mechanical engineering, physics, and chemical phys
ics. An instructor of a course in this subject matter is provided ample opportunity to limit, alter, or
expound on any part of the text material as needed to satisfy the course description and needs of
the students. Extensive glossaries of terms, expressions, and symbols at the end of the text aid in the
learning process.
As with any text dealing with complex subject matter, there will undoubtedly be found typos
and errors that were overlooked by the author. Hopefully, these have been kept to a minimum.
However, should any be found by the instructor or readers, the author would appreciate knowing of
them so that corrections can be made. The author may be contacted at the following email address:
rtinder@eecs.wsu.edu.
vii
Acknowledgments
The author is deeply indebted to the many senior and graduate students for their countless ques
tions, comments, arguments, and suggestions given during the many years that the contents of this
text were used as notes in the conduct of the authors graduate course taught at Washington State
University. As most professors know, students can and do provide the most candid and critical as
sessments of material presented in a given course. The author also acknowledges the suggestions
and contributions of Prof. Elias (Lee) Stefanakos to the subject matter presented in this text, in par
ticular, to the optical effects presented in Chapter 7. Dr. Stefanakos is director of the Clean Energy
Research Center at the University of South Florida.
Gratefully acknowledged is the encouragement and helpful suggestions offered by Joel Claypool,
publisher of Morgan & Claypool Publishers. Finally and most importantly, the author acknowledges
the support, care, and understanding of his loving wife, his best friend and condante, Gloria.
ix
Contents
PA RT I
CHAPTER 1
Introduction
Effect Tensor Cause
Tensor
Parameter
= Property
Tensor
Coefcient Parameter
(1.1)
or its inverse, which places the inverse of the tensor property coefcient on the lefthand side of the
equation.
The particular tensor property will have a denite physical signicance and will be represented
by a xed number of components depending on the nature and tensor character of the intensive
and extensive parameters that it relates. One physical signicance of the property coefcient may be
given as the rate of change of one parameter with respect to the other as implied by Eq. (1.1).
One or both of the parameters that dene the property coefcient will usually be a eld ten
sor such as stress or strain, electric or magnetic eld strength, or temperature (a scalar). The extent
to which a property of a crystal exists with respect to the application of a given eld depends on the
electronic and subatomic structure of the atoms and on the manner in which they are arranged in
the lattice.
Shown in Table 1.1 are four typical examples of properties of crystals that are directly related
by cause and effect tensor parameter. Here, the pyroelectric coefcient pi is a vectorscalar tensor
property, hence, a vector, that relates the change in polarization DPi with a change in temperature DT.
The thermal expansion coefcient Aij is a tensorscalar tensor property of tensor rank 2 that relates
a change in strain Eij with a change in temperature DT. The piezoelectric coefcient dijk is a vector
tensor property of tensor rank 3 that relates the polarization Pi to the stress tensor Sjk. Finally, the
elastic compliance coefcient sijkl is a tensortensor property of rank 4 that relates the stress Sij to
4 TENSOR PROPERTIES OF SOLIDS
TABLE 1.1: Typical examples of properties of crystals that are directly related by cause and
effect tensor parameters
CAUSE TENSOR
EFFECT TENSOR TENSOR PROPERTY TENSOR RANK OF
PARAMETER PARAMETER NAME EQUATION COEFFICIENT
the strain Ekl (Hookes law). Thus, it is seen that the tensor rank of a property coefcient is the sum
of the tensor ranks of the parameters that it relates. Note that all tensor property coefcients given
in Table 1.1 are examples of equilibrium properties. A wellknown example of a nonequilibrium or
transport property is resistivity Rij , a secondrank tensor that relates electric eld strength Ei to the
current density Jj according to Ei Rij Jj , which, of course, is the tensor representation of Ohms law.
The distinction between equilibrium and nonequilibrium transport properties will be made clear in
the section that follows, together with Parts I and II of this text.
Properties of crystals that represent timeindependent processes are called equilibrium proper
ties. Such properties can adequately be described phenomenologically by using equilibrium thermo
dynamics, that is, thermostatics. Properties that represent timedependent or spontaneous processes
are called nonequilibrium or transport properties. Such properties can be described only by use of
the thermodynamics of irreversible processes, a subject that is covered in Part II of this text.
The concept of thermodynamic reversibility is intimately connected with the concept of equi
librium. The term reversible applies to a process within a system that has been displaced from equilib
rium only to an innitesimal extent. Therefore, a reversible process may be dened as the hypothetical
passage of the system through a series of equilibrium states so close together that they are nearly indis
tinguishable. Such a process is reversed by an appropriate innitesimal change of the physical condi
tions imposed on the system. Actually, no ongoing process is reversible in the strict sense of the word.
However, if the conditions to be imposed on the system are applied innitesimally fast, then, within
experimental error, the process may be considered reversible. A reversible process is usually considered
to be a linear process over an innitesimal change in cause and effect parameters. However, a reversible
process may be nonlinear, provided that the innitesimal changes in the system are restored reversibly.
In the development of the equilibrium properties, we will assume that the reversible processes are lin
ear and that thermodynamic equilibrium is established at each point in an innitesimal change.
in this case, are the extensive parameters. Extensive parameters are those that depend on the amount
of material of the solid phase system. Parameters that are independent of the amount of material in
the solid phase are called intensive parameters and are associated only with the external conditions
(elds) imposed on the system. Thus, the arrows in Figure 1.1 are drawn from the intensive (inde
pendent) parameters to the extensive (dependent) parameters. Reversal of the arrows denes the set
of 16 rigidity effects that will later be shown as the collective inverse of the compliance effects.
For the convenience of the reader, the 16 compliance equilibrium properties are presented
in Table 1.2 in the order of increasing tensor rank, rst for the principle effects and then for the
Intensive Extensive
Parameters Parameters
T S
T emperature Entopy
(0) (0)
E P
Electric
Polarization
Field
(1)
(1)
B M
Magnetic
Magnetization
Flux
(1)
(1)
Stress Strain
(2) (2)
FIGURE 1.1: Generalized interaction diagram for the 28 rstorder effects showing the names, sym
bols, and tensor rank (in parentheses) for each of the 8 parameters.
INTRODUCTION 7
TABLE 1.2: The set of 16 compliance effects and their associated parameter pairs showing the
4 principal effects and 12 coupled effects as listed in the order of increasing tensor rank
Principal effects
(E, S) Elasticity 4
(E , E)
Converse piezoelectric effect (rstorder electrostriction) 3
Stress Elasticity, s (4) Strain
(2) (2)
FIGURE 1.2: Interaction diagram representing the thermal, thermoelastic, and elastic effects. The ar
rows point to the dependent variable.
interaction (coupled) effects. Note that each parameter pair is given in (extensive, intensive) nota
tion form.
Other equilibrium properties, not mentioned above, include those in Figure 1.1 for which no
oneway arrows are shown. Some of these are of little or no interest to the developments in this text.
Most of those equilibrium properties that remain are higherorder effects that can usually be dened
in Taylor series expansions of the appropriate parameters. The higherorder effects are usually of high
tensor rank and are, accordingly, more complicated. These include such effects as electrostriction, mag
netostriction, and a variety of optical effects. Many of these effects will be considered in later chapters.
To provide a little more background detail, we will next consider an interaction diagram asso
ciated with the thermal and mechanical variables, that is, one that represents the thermal, thermo
elastic, and elastic effects. This interaction diagram is shown in Figure 1.2 where the arrows again
point toward the dependent variables.
Noting from Figure 1.2 that both the stress and temperature elds contribute to an elastic
strain, we write in differential form,
or in integrated form
In these equations, sTijkl (uEij / uSkl)T is the isothermal (temperature independent) elastic compliance,
and ASij (uEij / uT )S is the isopiestic (stress invariant) coefcient of thermal expansion. The fourth
rank tensor property sTijkl represents a principal effect (elasticity) because it relates the conjugate pa
rameters S and E. The secondrank tensor property ASij , on the other hand, represents a coupled effect
(thermal expansion) because it relates the cross parameters T and E at constant stress, S.
By similar reasoning, one notes from Figure 1.2 that a positive increase in stress as well as an
increase in temperature and strain produces an increase in the entropy of a crystal. In differential
form, we write
or in integrated form
Here, ATij (uS / uSij )T is the isothermal piezocaloric coefcient, equal to the coefcient of thermal
expansion measured under constant stress, and C S T (uS / uT )S is the isopiestic (constant stress)
heat capacity. The fact that (uS / uSij )T (uEij / uT )S is a consequence of thermodynamic arguments
to be discussed in detail later.
The properties just described have been dened in such a way that only the intensive parame
ters are held constant. Other coupled effects result from an association of the thermal and mechani
cal variables but which will have both intensive and extensive parameters held constant. Suppose it
is desirable to equate the isothermal elastocaloric (heat of deformation) with the isometric thermal
stress coefcient as depicted by the vertical arrows in Figure 1.2. When this is done, we write
a result that follows from developments that will be presented later. Note that the isometric thermal
stress coefcient describes the negative or compressive stress produced when a mechanically con
strained crystal is heated. Equation (1.6) is one of many Maxwell relations to be discussed later in
Chapters 4 and 5.
uctuation theory, the principle of microscopic reversibility, and the Onsager reciprocal relations,
that is, through the use of the thermodynamics of irreversible processes. In contrast, the interactions
between equilibrium properties are easily deduced by using standard thermodynamic (thermostatic)
arguments.
Although it is not commonly done, the rstorder transport properties may also be repre
sented by interaction diagrams. To do this, it must be stated clearly that the use of such diagrams in
no way implies thermodynamic reversibility in the same sense as for the equilibrium properties, but
rather implies microscopic reversibility as used in uctuation theory. To construct a useful interac
tion diagram for rstorder nonequilibrium properties, three pairs of conjugate parameters that are
physically measurable are used. These pairs are the three current densities (uxes) and their conju
gate driving forces representing the ow of current ( J n, FE ), heat ( J q, FT ), and mass ( J m, FC ).
Shown in Figure 1.3 is the interaction diagram for the rstorder transport properties that positions
the temperature gradient (FT ), electric potential gradient (FE ), and concentration gradient (FC )
E
Electrical Cond., KnE
El
ec
tro
dif
)
=0
Kq E KmE
fu
siv
(J n
e
Po
er
ow
we
cP
r
(J
Jn
tri
m
l ec
=0
oe
)
erm
Th
KnT qT
Jq Jm KnC
K D if
ti v ity, fusi
uc vi ty,
Cond K mC
l
rma KmT K qC
Th e
T C
Thermodiffusive Power (J m = 0)
FIGURE 1.3: Interaction diagram for the rstorder nonequilibrium (transport) properties showing the
9 conductivities and 3 power coefcients, all 12 of which are secondrank tensor properties.
INTRODUCTION 11
in clockwise sequence on the outside of the interaction triangle. The heat current ( J q), electron
(or ion) current ( J n), and mass current densities ( J m) are placed inside the gradient triangle near
est their respective conjugate parameters. All transport parameters, it will be noted, are tensors of
6
rank 1, that is, vectors. This diagram represents n 1 (n
1) 15 relationships, which include nine
conductivities each relating a ux to a gradient, three power coefcients each relating one gradi
ent to another, and three relationships between the current densities. The 12 conductivities and
power coefcients are each secondrank tensors. The relationships between uxes are interpreted,
for example, as the heat or entropy associated with the ow of charge for the ( Jq , J n) relationship
and similarly for the two other pairs. These current density relationships have not been considered
as tensor properties.
There exist other transport properties not included in the interaction diagram of Figure 1.3.
These arise primarily from the application of magnetic and/or stress elds applied to crystals ex
hibiting one or more of the properties represented in the J
F interaction diagram. This leads
to important thermomagnetic and galvanomagnetic, piezoresistance, piezothermoelectric, and the
piezogalvanomagnetic effects and to other higherorder transport properties.
The phenomenological developments of the transport properties in crystalline solids are the
topics covered in Part II of this text. These properties will be discussed in some depth based on the
basic principles of irreversible thermodynamics. The treatment is, by its nature, more difcult than
that presented in Part I, dealing with the phenomenological developments of the equilibrium ten
sor propertiesthe basic principle of irreversible thermodynamics are statistical in nature, dealing
mainly with uctuation theory. Recognizing this, special care is taken to present the more complex
developments in a manner that minimizes this difculty.
13
CHAPTER 2
where summation from 1 to 3 with respect to the repeating (dummy) sufx, j, is understood. This
is called the Einstein summation convention, which allows the summation sign 3 to be dropped. Ex
panding Eq. (2.1), as required by summation, gives the following three equations for pi:
14 TENSOR PROPERTIES OF SOLIDS
p Tq . (2.4)
Vectors may be represented either by a (3 s 1 = rows s column) column matrix as in Eq. (2.3)
or as a (1 s 3) row matrix
p1
p2
p3
or [ p1 p2 p3] ,
depending on the type of matrix operation to be performed. The nine components of a second
rank tensor, Tij, may be represented by a (3 s 3) matrix as in Eq. (2.3) or as either a (9 s 1) column
matrix or (1 s 9) row matrix, as will be demonstrated later. In any case, it must be understood that
a matrix is nothing more than an array of symbols or numbers arranged in rows and columns. The
matrix array has no physical meaning in itself but may represent a tensor that does have physical
signicance.
ponents of a magnetic tensor change sign only if the atomic magnetic moments are reversed. Polar
tensors, on the other hand, are unaffected by either change in handedness or reversal of magnetic
moments. In this section, attention will be focused on the transformation laws of polar tensors.
or
in convenient tensor subscript notation. Here, the aij are called the direction cosines, for which exam
ples are shown in Figure 2.1. Thus, nine direction cosines are required to specify the transformation
of a polar vector where i and j represent the new and old axes, respectively.
Equations in (2.5) can also be conveniently represented in the matrix form
T1 a11 a12 a13 T1
T2 a21 a22 a23 T2
T3 a31 a32 a33 T3
(2.7)
or simply
T a aT (2.8)
16 TENSOR PROPERTIES OF SOLIDS
x3
T
x3' 1 a 33
c os
T3' T3
x2'
T2'
cos1a31
x2
T2
T1 cos1a13
co T1' 1 a 12
s
x1 s 1 co
a
11
x1'
FIGURE 2.1: Transformation of the polar vector T mT a showing sample direction cosines.
pa ap (2.12)
q a~qa (2.12a)
after which, by introducing Eqs. (2.11) and (2.12a) into Eq. (2.12), there results in matrix notation
T a aT a~ (2.13)
or
in tensor subscript notation. Both Eqs. (2.13) and (2.14) represent the transformation law for polar
secondrank tensors. In Eq. (2.14), the components of T ija are obtained by direct summation of the
repeating (dummy) subscripts k and l, whereas in Eq. (2.13), the same components are given in the
form
a11 a12 a13 T11 T12 T13 a11 a21 a31
T a21 a22 a23
a31 a32 a33
T21 T22 T23
T31 T32 T33
a12 a22 a32 ,
a13 a23 a33
(2.15)
~ ~
Tij (Tij Tji ) / 2 (Tij
Tji ) / 2 (T T ) / 2 (T
T ) / 2 Sij Aij , (2.16)
18 TENSOR PROPERTIES OF SOLIDS
T11 (T12 T21 ) (T13 T31 ) S11 S12
S31
~
S (T21 T12 )
)
T22
(T13 T31 (T32 T23 )
(T23 T32 )
T33 Sym.
S22
S23 S,
S33 (2.17)
0 (T12 T21 ) (T13 T31 ) 0 A12 A31
~
A (T21 T12 ) 0
(T31 T13 ) (T32 T23 )
(T23 T32 ) A12 0
0
A23 A.
A31 A23 0
(2.18)
Tensor notation S11 S22 S33 S23( S32 ) S31( S13 ) S12( S21)
Strain notation S1 S2 S3 2S23 2S32 2S12
Matrix notation S1 S2 S3 S4 S5 S6 (2.19)
S11
S22
S1
S2
S1
S2
S
S33
S23
S31
S
12
or
S3
2S4
2S5
2S
6
or
S3
S4
S5
S
6
(2.20)
or their (1 s 6) row transpositions. The single subscript form will be the form of choice for use in matrix
symbolic equations. The third form in (2.20) is also the accepted matrix form for the strain tensor.
Examples of symmetrical secondrank tensors are stress, strain, thermal expansion, dielectric
and magnetic susceptibilities, and others. From Eq. (2.18), it is clear that the principal components
INTRODUCTION TO TENSOR AND MATRIX REPRESENTATION 19
of an antisymmetrical secondrank tensor are null, leaving only three antisymmetrical components,
A23, A31, and A12. Examples of antisymmetrical secondrank tensors include the rotational com
ponent of a generalized elastic deformation leaving strain Eij Eji as a symmetrical secondrank
tensor.
Carrying out the indicated multiplication and arranging the components of S a and S into (6 s 1)
column matrices permits Eq. (2.21) to be represented in the quadratic form
2 2 2

2 2 2
S3 a11 a 32 a 33 2a32 a33 2a33a31 2a31 a32 . S3

S4 a21 a31 a22 a32 a23 a33 a22 a33 a23 a32 a21 a33 a23 a31 a21 a32 a22 a31 S4
S5 a31a11 a32 a12 a33 a13 a12 a33 a13 a32 a11 a33 a13 a31 a11 a32 a12 a31 S5
S6 a11 a21 a12a22 a13a23 a12 a23 a13a22 a11a23 a13 a21 a11 a22 a12a21 S6
or simply in symbolic matrix notation
Sa AS. (2.22)
Here, A is a (6 s 6) matrix called the quadratic transformation matrix for a symmetrical second
rank tensor and where the third single subscript notation of (2.20) has been applied. With few
exceptions, the property tensors of higher order, which are commonly encountered, are represented
by third and fourthrank tensors having some inherent symmetry. Thus, where it is necessary to
specify the transformation law for these matter tensors, rather extensive practical use will be made
of the A transformation forma method preferred over the more cumbersome method of direct
summation of the repeating sufxes in the tensor subscript forms.
20 TENSOR PROPERTIES OF SOLIDS
A mnemonic diagram for the quadratic transformation matrix A can be constructed by divid
ing it into four sections as follows:

of [aij ] matrix omissions of [aij ] matrix .

Product of column
omissions of [aij ] matrix
Cross product of
minor of element aij
The content of these four sections can be veried by an inspection of Eq. (2.22) in expanded form.
Not all property tensors exhibit inherent symmetry, and for this reason, a similar quadratic
transformation law must be written for an asymmetrical secondrank tensor. In this case, the trans
formation matrix becomes a (9 s 9) quadratic form. The development of this more general form
follows from Eq. (2.15) by carrying out the indicated multiplication and arranging the components
of T a and T as (9 s 1) matrices similar to (2.20) but with no symmetry. The result is given by
T aBT , (2.23)
where B is called the (9 s 9) general quadratic transformation matrix for asymmetrical secondrank
tensors presented in Eq. (9.31). The B transformation form is useful in describing the transforma
tion laws for the less common piezothermoelectric and elastothermoelectric power properties as
well as the piezomagnetoelectric and elastomagnetoelectric effects.
and
For the case where q is a symmetrical secondrank tensor (hence, q q~), it follows that for the trans
formations pa ap, qa Aq, and q A
1qa, there results
T a aTA
1, (2.26)
~ in general. In tensor subscript
where A
1 is the inverse of A and where it is understood that A
1 vA
notation, Eq. (2.26) is written as
The partial symmetry of T in Eq. (2.24) is implied by the symmetry of q. This is easily shown
by using tensor subscript notation giving
which permits
Tijk Tikj .
q1
q2
p1 T11 T12 T13 T14 T15 T16
q3
p p2 T21 T22 T23 T24 T25 T26
p3 T31 T32 T33 T34 T35 T36
q4
Tq,
q5
q
6 (2.30)
with respect to axes 0xi . Note that subscript m in Eq. (2.29) is unfolded according to the matrix
notation in (2.20). This permits a reduction in the T matrix from a (3 s 9) to a (3 s 6) matrix, as
given in Eq. (2.30), both of which avoid the need for a threedimensional representation.
The tensors Tijk and Tikj in Eq. (2.28) are called tensor isomers and represent a certain partial
symmetry. The tensor Tijk has a total of 3! = 6 isomers possible, which are obtained by the permuta
tion of pairs of subscripts. In comparison, the transpose of a secondrank tensor Tij is its only isomer.
Examples of thirdrank tensor properties that exhibit this partial symmetry are the piezoelectric
22 TENSOR PROPERTIES OF SOLIDS
effect, rstorder electrostriction, piezomagnetic effect and rstorder magnetostriction, the linear
electrooptical effect, the thermalelectrooptical effect, and others.
The transformation of components for the partially symmetrical thirdrank tensor Tijk Tikj
is carried out in accordance with Eq. (2.26) for new and old sets of axes, 0xai and 0xi , respectively:
1
11
1
21
1
12
1
22
1
13
1
23
1
14
1
24
1
15
1
25
1
16
1
26
a11 a12 a13 T11 T12 T13 T14 T15 T16
1 1 1 1 1 1
31 32 33 34 35 36
T a21 a22 a23 T21 T22 T23 T24 T25 T26
a31 a32 a33 T31 T32 T33 T34 T35 T36
1
41
1
1
42
1
1
43
1
1
44
1
1
45
1
1
46
1
51 52 53 54 54 56
1 1 1 1 1 1
61 62 63 64 65 66
T a aTA 1 (2.31)
It may be recalled that the inverse (or reciprocal) A
ij1 of a matrix A is the transpose of the
cofactor (Aij ) of the element Aij divided by the nonzero determinant of Aij . That is,
( Aji) ( A~ )
(Aij )1 or A (2.32)
Aij A
where (Aij ) (
1)(i j )\Mij \ is the cofactor of element Aij and \Mij \ is its minor (the determinant that
remains after removing the ith row and jth column in \Aij \ ).
Obviously, transformation of tensors of rank 3 can be quite laborious. Fortunately, the linear
and quadratic transformation matrices representing the symmetry operation for crystals are rela
tively uncomplicated. As will be shown later in Section 3.5, these matrices often consist of compo
nents that are 0, 1, or 1, and in most cases, A
1 A ~, a result that is not true generally.
and
If both p and q are symmetrical secondrank tensors, convenient use can again be made of the A
quadratic transformation form. Because p and qa transform as pa Ap and q A
1qa then
or
T a ATA 1 (2.35)
as the transformation equation for T in matrix symbolic notation. In tensor subscript notation, Eq. (2.35)
becomes
The partial symmetry of Tijkl is implied by the symmetry of pij pji pm and qkl qlk qn where it is
now proper to write
The partial symmetry expressed by Eq. (2.37) permits a reduction in the number of indepen
dent coefcients needed to specify T from 3(4) 81 to 36. Because both p and q are represented by
(6 s 1) matrices, it follows that T must be a (6 s 6) matrix and that Eq. (2.37) can be presented as
p1
p2
T21
T11 T12 T13 T14 T15 T16 q1
T22 T23 T24 T25
T26 q2
p3 T31 T32 T33 T34 T35 T36 . q3
p4 T41 T42 T43 T44 T45 T46 q4
p5 T51 T52 T53 T54 T55 T56 q5
p6 T61 T62 T63 T64 T65 T66 q6
(2.38)
Just as for the case of the partially symmetrical thirdrank tensor, the transformation law for
the partially symmetrical fourthrank tensor in Eq. (2.37) is most conveniently represented in ma
trix form according to T a ATA
1 in Eq. (2.35), giving
24 TENSOR PROPERTIES OF SOLIDS
11
21
12
22
13
23
14
24
15
25
16
26
T11
T21
T12
T22
T13 T14
T23 T24
T15
T25
T16
T26
1
11
1
21
1
12
1
22
1
13
1
23
1
14
1
24
1
15
1
25
1
16
1
26
1 1 1 1 1 1
32 33 34 35 36 T31 T32 T33 T34 T35 T36 31 32 33 34 35 36
T 31
1 1 1 1 1 1
41 42 43 44 45 46 T41 T42 T43 T44 T45 T46 41 42 43 44 45 46
1 1 1 1 1 1
51 52 53 54 55 56 T51 T52 T53 T54 T55 T56 51 52 53 54 54 56
1 1 1 1 1 1
(2.39)
61 62 63 64 65 66 T61 T62 T63 T64 T65 T66 61 62 63 64 65 66
Here again, it is shown that numerical manipulation required to transform a higherrank ten
sor is considerable, particular for an arbitrary rotation of axes. In such cases, use of the computer is
recommended. However, as pointed out earlier, transformation matrices representing most crystal
symmetry operations are strikingly simple, allowing tensor transformations in most cases to be car
ried out with little difculty by using A
1 A~ in Eqs. (2.31) and (2.39) or even by the method of
direct inspection discussed later.
The maximum inherent symmetry possible for fourthrank tensors is given by
In this case, the leading diagonal of components becomes the mn = nm symmetry line. This elimi
nates the 15 coefcients below the leading diagonal symmetry line as independent components.
The remaining 21 coefcients are now represented by the symmetrical (6 s 6) matrix
T33 T34 T35 T36
[Tmn ] [Tnm ]
T44 T45 T46
(Sym.) T55 T56
T66 (2.41)
The symmetrical matrix of Eq. (2.41) is used to represent the elastic compliance and stiffness
moduli as well as the many properties involving these moduli. The inherent symmetry expressed by
Tmn Tnm results solely from thermodynamic arguments that are presented in Section 4.4.
Property tensors with tensor rank greater than four are not as common as some of those
of lesser tensor rank. Nevertheless, a few fth and sixthrank tensor properties have either been
measured experimentally or have been predicted to exist on theoretical grounds. Examples are the
fthrank piezoelectrooptical, piezomagnetooptical, and sixthrank quadratic piezooptical ef
fects mentioned in Section 7.3.2 and the quadratic piezothermoelectric power and quadratic piezo
INTRODUCTION TO TENSOR AND MATRIX REPRESENTATION 25
TABLE 2.1: The transformation laws for polar tensors up through the rank 4 showing tensor rank,
tensor subscript notation, matrix symbolic notation, and the referred matrix text equation.
TRANSFORMATION LAW
0 Ta T
1 T ai aijTj T a at (2.8)
resistance effects represented in Eqs. (9.26) and (9.38), respectively, both of which are sixthrank
tensor properties.
with some exceptions. The subjects of axial tensors, tensor differentiation, tensor eld subject mat
ter, and the vector cross product will be reviewed later in Sections 2.4, 2.5, and 2.6, respectively.
This requires that R11 A11 B11, R22 A22 B22 , R12 A12 B12 for all six independent compo
nents of the resultant matrix R. The sum rule may be generalized by the equation
which is restricted to components of tensors having the same rank and tensor character. The sum
rule obeys the commutative, associative, and distributive laws of additions wellknown in Cartesian
algebra.
These laws are written in the order of increasing extent to which they are obeyed by the tensor
multiplication operations. Generally speaking, the distributive law is always obeyed if the sum rule
is obeyed, the associative law is obeyed if the permutation tensor is not involved, and the commu
tative law is never obeyed except for scalar products. The tensor representation of the vector cross
product and the properties of the Kronecker delta and permutation tensor will be reviewed later in
Section 2.6.3.
INTRODUCTION TO TENSOR AND MATRIX REPRESENTATION 27
or
~
Note that if B v B , then the product AB yields a (3 s 9) matrix.
The outer product rule can be generalized by the tensor subscript equation
where R has a tensor rank equal to the sum of the ranks of A and B, that is, rR rA rB , a fact that
is lost in the use of symbolic matrix notation R AB.
or R = AB in tensor symbolic notation. Here, R is a tensor of rank rR (rA rB)
2 having the same
tensor character as that of A and B. As an example, consider the single contraction (inner) product
of a polar vector and a partially symmetrical thirdrank polar tensor (Bijk Bikj) given by
28 TENSOR PROPERTIES OF SOLIDS
or
Rm Ai Bim (i 1 3; m 1 6)
B11 B12 B13 B14 B15 B16
R [A1 A2
A3 ] B21 B22 B23 B24
B31 B32 B33 B34
B25
B35
B26 [R1 R2 R3 R4 R5 R6 ],
B36
which yields the components of symmetrical polar secondrank tensor R in the form of a (1 s 6)
matrix.
Double contraction results when two subscripts in the product of two tensors of the same
rank r are set equal, producing a tensor of rank r
4. The double contraction product of two tensors
of arbitrary tensor rank is generalized in tensor subscript notation as
or R = A B in tensor symbolic notation. Here, R is a tensor of rank rR (rA rB)
4 having the same
tensor character as that of the A and B combination. An example of double contraction is
which was used in Eq. (2.33) to represent a polar fourthrank that relates two polar secondrank
tensors.
Tensor contraction continues through triple, quadruple, etc. contractions and becomes com
plete when the product of two tensors of the same rank yields a scalar. This product is called the
scalar product, which is generalized as
called the trace of AB. An example is the scalar product of two symmetrical secondrank tensors,
R Aij Bij ,
INTRODUCTION TO TENSOR AND MATRIX REPRESENTATION 29
B1
B2
R [A1 A2 A3 A4 A5 A6]
B3
B4
B5
B6
tr(AB)
Here, for example, the handedness factor \a \ for a secondrank tensor is the determinant of the
transformation matrix (aij ) given symbolically by
 
a b c
g h i h i
     
a  = d e f = a . e f b . d f + c . d e
g i g h
and axialmagnetic but which can be represented as a polarmagnetic secondrank tensor as dis
cussed in Section 10.3. The reader must be aware of the fact that axial tensors and antisymmetrical
tensors are two entirely different tensor characteristics the distinction of which will be made evident
in Section 2.6.3. Magnetic tensor character is discussed in Appendix A.
n
1
0 0
f (P,
i
Qj
, Rkl
...)
0(
n (Pi Pi ) Pi (Qj Qj Qj (Rkl R kl )Rkl f (Pi0, Qj0 , Rkl0 ...), (2.52)
n0
where n 1, 2, 3,... is an integer and f (P i0, Q 0j , Rk0l ...) signies that after the function is operated on,
the resulting coefcients are evaluated at the reference values of Pi Pi0, Qj Q j0, Rkl Rk0l , and so
forth. Because the function f may itself be a tensor quantity of arbitrary tensor rank, the resulting
coefcients are tensors given in accordance with the tensor differentiation laws
2
A...ij A...ij
T...ijkl ... ,U...ijkl ...rs... . . . , et
Bkl... Bkl... Crs... D,E,...
C,D,... (2.53)
Here, the law expressed by T...ijkl... implies that all remaining components of B and all components
of C, D, and so forth are held constant and that T...ijkl... has the tensor rank rA rB and the combined
tensor character of A and B. The law expressed by U...ijkl...rs... for a secondorder derivative implies
that U has a tensor rank of rA rB rC with the combined tensor character of A, B, and C, where it
is understood that the remaining components of B and C and all components of D, E, and so forth
are held constant. Notice that our rule of subscript order is read from toptobottomlefttoright.
However, because other subscript order schemes can be found in literature, care must be taken to
recognize which scheme is used.
INTRODUCTION TO TENSOR AND MATRIX REPRESENTATION 31
As an example of the use of Eq. (2.53), let the electric polarization Pi be a function of electri
cal eld strength Ej and stress Skl and let Pi (Ej , Skl ) be expanded in a Maclaurin series (special case
of a Taylor series) about the state of zero electric eld and zero stress to give
n
1
Pj(Ej, kl ) E Pi (0,0),
n j Ej
n=0 (2.54)
2
P P Pi
kl 1 E E
Pj(Ej,
kl ) Pi (0,0) i Ej i Ej Em
Ej
kl
(0,0) (0,0) 2
j m (0,0)
2Pi 2Pi
2 Ej
kl
kl
n o
Ej
kl
(0,0)
kl n o (0,0)
As will be shown in later chapters, the various coefcients (in parentheses) dene certain ten
sor properties. For example, K0
1(uPi / uEj ) Cij is the dielectric susceptibility tensor for a crystal and
K0 is the permittivity in a vacuum. The quantity (uPi / uSkl) dikl is the piezoelectric tensor. Here,
both Cij and dikl are rstorder (n = 1) effects evaluated, in this case, at zero electric eld and zero
stress. The three properties given within the square brackets are secondorder (n = 2) effects and are
represented by third, fourth, and fthrank tensors also evaluated at zero electric eld and zero
stress. Note that had the expansion in Eq. (2.54) also been taken about the state of reference tem
perature T 0, it would be called a Taylors serieshence, the basic distinction between a Maclaurins
series and a Taylors series.
ijk ...
Tijk ... pst = pst ...ijk ... =
xpxsxt ... (2.55)
or written as gradF F in vector symbolic notation. See Eq. (8.1) in Chapter 8 as an example. The
gradient of a scalar points in the direction of the maximum rate of change and that has a magnitude
equal to that maximum rate of change. Examples of a scalar eld are the electrostatic potential (or
voltage), chemical potential, and temperature. Thus, the gradient of any scalar eld is always from
low to high potential as, for example, from low to high temperature. Thus, Fouriers law requires
that the heat must ow from high to low temperature in a direction opposite to the temperature
gradient, hence, the minus sign in Eq. (8.7) presented in Part II of this text.
Application of Eq. (2.55) to the eld vector Yi(x) results in the asymmetrical dyadic
ujYi uYi /uxj called the vector gradient of the given eld with components given by a 3 s 3 Jacobian
matrix,
11 / x1 11 / x2 11 / x3
i
Tij
xj
22 / x1 22 / x2 22 / x3
33 x1 33 x2 33 x3
/ / / (2.57)
We will have no further need to apply Eq. (2.55) to tensor elds of tensor rank greater than r 1.
INTRODUCTION TO TENSOR AND MATRIX REPRESENTATION 33
ijk...
Tjk ... = iijk ... = xi (2.58)
or as T divY = Y in tensor symbolic notation. Contraction can be carried out on any of the
indices of Yijk...(x), but the results will, in general, be different.
A physical interpretation of Eq. (2.58) is reasonably straightforward. The divergence of a
tensor gives at each point the rate per unit volume at which the physical entity represented by Y is
issuing from that volume. The divergence theorem (also known as Gauss theorem) is widely used and
provides the integral denition of divergence of a tensor eld given by
dS .
div lim s
V0 V (2.59)
where O sdS.Y is called the net ux of Y out of S. Thus, Eq. (2.59) denes the divergence of a tensor
eld at a point P in V as the limiting value of the ux of Y per unit volume out of S when $V m0.
The simplest example is the divergence of a vector eld Yi(x) equal to a scalar uiYi having
magnitude
1 2 3
i i = + + = tr(ji ),
x1 x2 x3 (2.60)
which is equal to the trace of the vector gradient in Eq. (2.57). A wellknown example of the appli
cation of Eq. (2.60) is the steady state in a thermoelectric system when the divergence of the energy
ux vanishes, that is, .J u 0. This means that the heat energy emitted to the surroundings, say, by
Joule (I 2Rtype) heating in a volume element must be exactly balanced by the heat energy absorbed
by that volume element from the surroundings.
Now, if Ti is the ith component of a vector, then with the denitions of Eqs. (2.61), there results
the expressions Dij Ti Tj and Dij Tj Ti , or for a tensor Tjk , there results Dij Tjk Tik and Dij Tik
Tjk . All express the substitution property of the Kronecker delta, which will be used in Section 9.3 of
this text.
The permutation tensor eijk (also called the LeviCivita tensor, alternating tensor, or etensor)
is an antisymmetrical, axial, thirdrank tensor dened by
1 if ijk is an even permutation of 123
eijk 1 if ijk is an odd permutation of 123
if any two subscripts are the same (2.62)
m m m
A common application of eijk is the vector cross product or R B s C described by the equation
given in tensor notation
The three components of Ri are readily found by expansion of Eq. (2.63) or by using the
matrix form
B1C1
B2C2
B3C3
R1 0 0 0 1 0 0 1 0 0 B2C3 B2C3 B3C2
R2
R3
0 0 0 0 1 0 0 1 0 B2C1 B3C1 B1C3
0 0 0 0 0 1 0 0 1 B1C2 B1C2 B2C1
B3C2
B1C3
B2C1 (2.64)
Equations in (2.64) can be represented simply by R e(BC) in matrix symbolic notation, where the
dyadic product (BC) has been unfolded as the 9 s 1 form of Tij in Eq. (2.3). The top row of the [3 s 9]
matrix is unfolded as 111, 122, 133, 123, 131, 112, 132, 113, 121, then 211, 222, 233, 223, 231, 212,
232, 213, 221 for the second row, and 311, 322, 333, 323, 331, 312, 332, 313, 321 for the third row.
The difference between the antisymmetrical and axial character of a tensor is nicely described
in terms of the etensor. The permutation tensor has been described as antisymmetrical. This is true
by virtue of the fact that if any two subscripts of the component eijk are set equal, the component
becomes zerothe antisymmetrical property. The etensor is also axial due to the fact that if any
two subscripts are interchanged, which is equivalent to reversing the handedness of the axes, the
INTRODUCTION TO TENSOR AND MATRIX REPRESENTATION 35
value of the etensor changes sign, 1 to
1, or vice versa. These special features of the etensor will
be useful in dealing with the magnetooptical and galvanomagnetic effects discussed in Sections
7.3.4 and 10.2.
A generalization of the single contraction product involving eijk without restriction on tensor
rank and character is given by
or simply by A e . T in tensor symbolic notation. This equation states that a tensor T of rank r can
be represented by its dual A of rank r 1. Here, A has the combined tensor character of e and T but
retains the physical properties of T. Thus, if T represents an axial secondrank tensor (e.g., the mag
netoelectric susceptibility discussed in Section 4.5, then A must be an antisymmetrical (nonaxial)
tensor with the physical properties of T. A common application of Eq. (2.65) is the case where an
axial vector is converted to an antisymmetrical secondrank tensor given by
Ajkeijk Ri (2.66)
A generalization of double contraction product involving eijk can be represented, with certain
restrictions to tensors of arbitrary tensor rank and character, by the equation
or simply by A e : T in tensor symbolic notation. Here, the tensor rank of A is r
1 when the tensor
rank of T is r. The restrictions imposed on Eq. (2.67) are simply that tensor T must be of second
rank or higher and that it must be antisymmetrical in j and k if it is necessary that all components of
~
T be retained by A in the conversion. Thus, as an example, eijk Sjk 0 if S S . As a second example,
the reverse conversion to Eq. (2.66) permits an antisymmetrical secondrank tensor to be converted
to an axial vector expressed as
Or, as a third example, if T is an antisymmetrical thirdrank tensor in j,k only but is also axial,
then A must be a polar (true) secondrank tensor as expressed by
Here, A is said to be the dual of T. Equation (2.69) will nd use in Section 10.3 when dealing with
the Hall tensor.
36 TENSOR PROPERTIES OF SOLIDS
Further tensorial contraction using the permutation tensor is possible by highly restricted. A
m m m
common example is the triple scalar product V a s b . c , which represents the volume of a general
m m m
parallelepiped of sides a , b , c In tensor notation, this scalar product is simply written as
Veijk ai bj ck (2.70)
Thus, V does not transform as a simple scalar but rather as a pseudo (axial) scalar according to
V a aV.
ABG
The generalized Kronecker delta denoted by Dijk eABGeijk $K is given by the matrix
i j k
K i j k
i j k
(2.71)
such that the contraction products follow Section 2.3.4, leading to the matrix for triple contraction
given by ee~ 2tr(ee~) 6 as used in Section 7.3.4.
37
CHAPTER 3
3.1 INTRODUCTION
In the previous chapter, it was shown that the possession of inherent symmetry by a tensor of rank r
had the effect of reducing the number of independent components representing it from 3(r) to some
number that was determined by the number of indices that could be interchanged. In this section,
we will discuss certain additional limitations placed on the relationships between the components
of a tensor property by the structural symmetry of the crystal within which the property is manifest.
Remember, however, that not all tensors are affected by crystal symmetry. Secondrank eld tensors
such as stress and strain possess certain intrinsic symmetry, but their components are unaffected by
the symmetry of the crystal. On the other hand, property tensors, which may relate two or more
eld tensors and hence possess their intrinsic symmetry, will also acquire the symmetry of the crystal
within which the property is evinced. Thus, property tensors may possess a higher symmetry than
that possessed by the crystal.
When the components representing a given property tensor vary with crystallographic direc
tion, the crystal is said to be anisotropic with respect to that property. Conversely, if the components
of a given property tensor are invariant with crystallographic direction, the crystal is said to be
isotropic with respect to that particular property. A crystal may possess partial isotropy with respect
to a given property if, for example, the components of the property are invariant with direction in a
particular crystallographic plane but vary with direction out of that plane.
The term crystal symmetry, as used above, refers not to the atomic structure but to the mor
phology or macroscopic symmetry of the crystal. During the natural growth of some crystals, the
planes of highest atomic density have a propensity to form the external faces of the crystal. A
naturally occurring quartz crystal is a good example. The special relationship between these faces
produces a symmetry that forms the basis of classication of crystals into 32 conventional sym
metry classes called point groups. Thus, each of the 32 point groups denes a symmetry class. It is
the point group symmetry (i.e., macroscopic symmetry) of a crystal that imposes certain limitations
on the relationships between different components of a macroscopic tensor property. For magnetic
38 TENSOR PROPERTIES OF SOLIDS
crystals, the atomic magnetic spin moments, viewed collectively over the crystal, become important
in symmetry considerations. This leads to the formation of the 90 magnetic point groups. There are,
however, certain microscopic symmetry elements that take place at the atomic level and that are not
possible in a point group, conventional or magnetic. Several symmetry operations at the atomic level
are used to classify the microscopic symmetry elements in a threedimensional space lattice, and
these are called a space group. There are 230 conventional space groups and 1651 magnetocrystalline
space groups, and every crystal must belong to one or more of these groups. We will not further
consider space groups, conventional or magnetic, since they fall outside the scope of this text.
n 1 2 3 4 6
z
x
x2
y y
x
x1 z
The two operations, an nfold proper rotation and a center of symmetry, may be combined
to produce rotoinversion axes designated by x 1, 2, 3, 4, or 6. The rotoinversion operation is one of
nfold rotation followed by inversion through a center of coordinates. If the transformation matrices
for these two operations are a1 and a2 (
Dij), respectively, then the resultant transformation matrix
is a a2a1 (
Dij)a1
a1. A twofold rotoinversion axis of symmetry, 2 , is identical to a reection
across a mirror plane (sometimes called a plane of symmetry) lying perpendicular to the 2 axis. This
is illustrated in Figure 3.2, where the symbol commonly used to designate a plane of symmetry is
m ( 2 ).
As an example, the rotoinversion transformation matrix representing a reection across the
mirror plane x1, x2 is
1 0 0 1 0 0 1 0 0
1 0 0
a ( ij ) 0 1
0 0 1
0
0 0 1 0 0 1
0 1 0 0 1
0 0
0
1
0
0 ,
1 (3.1)
180o
Begin
Mirror Plane
End
which is obvious from an inspection of Figure 3.2. Here, the rst and second matrices represent a
center of symmetry and a 180o rotation about the 0x3 axis, respectivelythe order is immaterial.
Remember that the entries (1s,
1's, and 0's in this case) in a transformation matrix represent the
direction cosines as illustrated in Figure 2.1.
Other combinations of the two fundamental symmetry elements are possible and are desig
nated by certain symbology. An nfold rotoinversion axis lying in a plane of symmetry is designated
as X m = nm. An nfold rotation axis of symmetry perpendicular to a plane of symmetry is desig
nated as X/m = n/m. As an example, consider a fourfold rotation axis of symmetry about 0x3 lying
normal to the x1, x2 plane of symmetry. This symmetry operation designated as 4/m( 42), has a
transformation matrix
1 0 0 0
1 0 0 1 0
a 0
0
1
0
0 1
1 0
0
0 1
0 0
0 1 0 0 ,
1 (3.2)
TABLE 3.2: Symmetry transformation symbology used to identify the 32 point groups
X/mmm Rotation axis with one mirror plane normal to it and one mirror plane parallel to it*
*The last element in three and fourelement forms such as Xmm and X/mmm is usually unnecessary to generate the group (see
Table 3.6 for examples).
CRYSTAL SYSTEMS, SYMMETRY ELEMENTS, AND SYMMETRY TRANSFORMATIONS 41
and the 4/m point group would be generated by repeated operations represented by the above transfor
mation matrix product. The symbology used to identify the 32 point groups is presented in Table 3.2,
where X and n are interchangeable, and all rotations are taken to be CCW (positive rotations).
c
b y
a
FIGURE 3.3: General space lattice showing the primitive translation vectors and angles.
42 TENSOR PROPERTIES OF SOLIDS
membership in each system. The lattice symbols P, F, I, C, and R are the HermannMauguin nota
tion for primitive (P), facecentered (F), bodycentered (I), basecentered (C), and rhombohedral
(R) unit cells. Thus, a given crystal system may exist as more than one Bravais lattice. For example,
the orthorhombic crystal system exists in primitive, facecentered, bodycentered, and basecentered
crystal structures.
The space lattice is then generated by the translation vector
m m m m
T ma pb q c , (3.3)
where m, p, and q are integers. The totality of all such translation operations for all values of m, p,
and q is called the translation group of the crystal. The magnitudes (a, b, and c) of primitive transla
m m m
tion vectors a , b , c are called the lattice parameters, which, together with the lattice angles (A, B, G),
dene the unit cell of a crystal.
Before continuing with the subject of macroscopic crystal symmetry elements and symmetry
transformations, it will be instructive to review the notation for describing crystallographic planes
and directions. Shown in Figure 3.4 are the generalized Miller and MillerBravais indices for planes
and directions for the six crystal systems in Table 3.3 where the hexagonal and trigonal systems are
treated together.
Here, referring to Figure 3.4(a), the Miller indices for the plane (hkl ) are the reciprocals
of the intercepts (1 / ix , 1 / iy , 1 / iz ). For example, if the intercepts are (ix 1, iy 1, iz 1), then
z z
(hkl) Plane (hkil) Plane
iz
[UVTW]
[uvw] y'
Direction
Direction
y 120o y
o
iy 12 0
ix
(a) (b)
x x
Miller Indices MillerBravais indices for
for all crystal hexagonal and trigonal
systems crystal systems
FIGURE 3.4: Notation for description of planes and directions showing Miller indices for all crystal
systems and the MillerBravais indices for the hexagonal and trigonal crystal systems.
CRYSTAL SYSTEMS, SYMMETRY ELEMENTS, AND SYMMETRY TRANSFORMATIONS 43
TABLE 3.3: The 14 Bravais lattices showing the conventional unit cell axes and angles together
with their lattice symbols and minimum symmetry elements
MINIMUM
CRYSTAL UNIT CELL AXES AND LATTICE SYMMETRY
SYSTEM ANGLES SYMBOLS ELEMENTS
taking the reciprocals of the intercepts gives (111) for the plane. As a second example, if the inter
cepts are (ix 1, iy 1/2, iz 1/3) along axes 0x, 0y, and 0z, respectively, then the Miller indices for the
plane would be (1, 2, 3). For the hexagonal and trigonal crystal systems represented in Figure 3.4(b),
the i index in (hkil ) is determined by i
(h k) but is sometimes replaced by a dot as (hk.l ).
The Miller indices for direction [uvw] are found by walking along all axes, x, y, and z in
turn, from origin to the end of the lattice vector. Referring to Figure 3.3, one would measure dis
tances along x, y, and z axes in units of a, b, and c, respectively, or their fractions. As an example, and
again referring to Figure 3.3, a lattice vector represented by a, b, c would be designated by [111], or
a lattice vector (1/2)a,
b, 0 in the xy plane would be designated as [1/2, 1, 0] or clearing fractions
[1, 2, 0]. Referring to Figure 3.4(b), the same direction in the hexagonal and trigonal systems would
be designated as [UVTW ] [1, 2 , 1, 0], where T
(U V ). In the cubic system, for which a b c,
any direction [uvw] is perpendicular to the plane (hkl ) of the same indices. Planes of the form
are designated as {hkl} and {hkil }, whereas the directions of the form are indicated as uvw and
UVTW . The four index forms apply specically to the hexagonal and trigonal systems. The num
ber of nonparallel planes of the form {hkl } is found by multiplying [permutation term] s [sign
term]/2. For example {123} has [3!][23]/2 = 24 nonparallel planes of this form. Directions of the
form 123 also have 24 nonparallel directions of that form.
44 TENSOR PROPERTIES OF SOLIDS
INTERNATIONAL
CRYSTAL GROUP (SHORT)
SYSTEM NUMBER NOTATION
Triclinic 1 1
2 \\1 \\
Monoclinic 3 2
4 m
5 \\2/m \\
Orthorhombic 6 222
7 mm2
8 \\mmm\\
Tetragonal 9 4
10 4
11 \\4 /m \\
12 422
13 4mm
14 4 2m
15 \\4 /mmm \\
CRYSTAL SYSTEMS, SYMMETRY ELEMENTS, AND SYMMETRY TRANSFORMATIONS 45
INTERNATIONAL
CRYSTAL GROUP (SHORT)
SYSTEM NUMBER NOTATION
Trigonal 16 3
(rhombohedral)
17 \\3 \\
18 32
19 3m
20 \\3m \\
Hexagonal 21 6
22 6
23 \\6/m \\
24 622
25 6mm
26 6 m2
27 \\6/mmm \\
Cubic 28 23
(isometric)
29 \\m3 \\
30 432
31 4 3m
32 \\m3m \\
46 TENSOR PROPERTIES OF SOLIDS
where p is an integer representing the repeated twofold rotation operation and P = 180o. Clearly,
cos( pP)
1 for p p1, p3, p5... , and the transformation for 2/m above becomes (Dij), proving
that 2/m contains a center of symmetry and is represented by \\2/m \\ in Table 3.4.
The symmetry elements of any physical property of a crystal must include all the symmetry
elements of the point group of the crystal.
This means that the component of a tensor representing a property must remain invariant under a
transformation of coordinates governed by a symmetry operation valid for the point group of the
crystal. Mathematically, this is represented as
TABLE 3.5: The 10 possible generating matrices are shown for both the s and S forms
Center of symmetry, ~ = I
S
1 S
1 0 0 0 0 0
1 0 0 0 1 0 0 0 0
(1)
s (1 ) 0 1 0
0 0 1
(1)
0
0
0 1 0 0
0 0 1 0
0
0
I
0 0 0 0 1 0
Direct inspection method: 0 0 0 0 0 1 I is the identity
1m
1, 2m
2, 3m
3 (unit) matrix
0 0 1
(2 )
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
Direct inspection method:
0 0 0 0 0 1
1m
1, 2m2, 3m
3
s (7) (3z) 3/2 1/2 0
0 0 1
(7)
0
0
0
0
1 0 0
0 1/2 3/2
0
0
3 and 3
0 0 0 3/2 1/2 0
Direct inspection method: not
3/4 3/4 0 0 0 1/2
applicable
s (4x) 0 0 1
0 1 0
(8)
0 1 0 0 0 0
0 0 0 1 0 0
0 0 0 0 0 1
Direct inspection method: 1m1, 0 0 0 0 1 0
2m3, 3m
2
s (4z) 1 0 0
0 0 1
(9 )
0 0 1 0 0 0
0 0 0 0 1 0
0 0 0 1 0 0
Direct inspection method: 0 0 0 0 0 1
1m2, 2m
1, 3m3
If, on the other hand, a particular component of a tensor changes sign after such a transformation
of coordinates, the component must vanish for that crystal in accordance with Neumanns principle.
Mathematically, this is expressed as
for axial tensors, where \s\ is the determinant of the symmetry operator (see Section 2.4).
For a given crystal class, there will be as many sets of equations for each property tensor
as there are symmetry operations valid for the point group of that class. However, the number of
operators derived from these symmetry operations can be reduced considerably to some minimum
number required to generate the point group. These are called generation operators, which result
from the 10 (s) generating matrices given in Table 3.5. The S generating matrices are the quadratic
forms of the s matrices and are applicable only to symmetrical property tensors as represented by
~(0)= I are
Eq. (2.22) in Section 2.2.5. We note here that s(0) (1) (Dij), S(0) = I, and [S(0)]
1 S
identity (unit) matrices.
The minimum number of generating matrices (derived from the 10 generating matrices in
Table 3.5) required for each of the 32 point groups are given in Table 3.6. The point groups are
designated by using the international shortform symbology as used in Table 3.4. The generating
matrices will be used to determine the nonzero components of a given property tensor as required
for a particular point group and in accordance with the appropriate transformation law. The symbol
\\X \\ appearing in Table 3.6 is used to designate the holohedral group dened earlier. The mini
mum generating matrices can also be used to generate the stereograms for the 32 point groups (see
Endnotes).
The work required for simplifying the components of a given tensor can be greatly reduced
by recognizing that a tensor of rank r transforms like the products of r coordinates of a point. For
example, the centerofsymmetry operator s(1) (
Dij ) requires that
50 TENSOR PROPERTIES OF SOLIDS
INTERNATIONAL MINIMUM
CRYSTAL SYMBOL GENERATING
SYSTEM (SHORT FORM) MATRICES
Triclinic 1 s(0)
\\1 \\ s(1)
Monoclinic 2 s(2)
m s(5)
Tetragonal 4 s(9)
4 s(11)
4 2m s(12), s(11)
INTERNATIONAL MINIMUM
CRYSTAL SYMBOL GENERATING
SYSTEM (SHORT FORM) MATRICES
Trigonal 3 s(7)
\\3 \\ s(13)
32 s(12), s(7)
3m s(4), s(7)
Hexagonal 6 s(14)
6 s(15)
6 2m s(4), s(15)
4 3m s(16), s(10)
This means that for a polar property tensor of odd rank, any combination of subscripts will result in
T a
T 0 in accordance with Neumanns principle. Similarly, for an axial property tensor of even
rank, any combination of subscripts will result in T a
T 0 also in accordance with Neumanns
principle. This process of simplication is called the method of direct inspection and is applicable to all
point groups except those in the trigonal and hexagonal crystal systems. For a particular crystal class
in these two systems, it is necessary to operate on a property tensor with each generating matrix in
turn. The use of the quadratic generation operators is then recommended, especially for property
tensors of rank greater than two. Note that throughout this text, the notation for crystallographic
axes will adhere to the accepted convention x1 x, x2 y, and x3 z in accordance with Figure 3.1.
1. Triclinic system: Because all symmetrical secondrank property tensors are centrosym
metrical, they cannot be made null by the centerof symmetry operation. The symmetry
transformation becomes
S11 S12 S31
(1) (1)
S' s Ss S S12 S22 S23
S31 S23 S33
(3.10)
leaving the property Sij unchanged, with all six independent components needed to repre
sent it.
CRYSTAL SYSTEMS, SYMMETRY ELEMENTS, AND SYMMETRY TRANSFORMATIONS 53
(2)
2. Monoclinic system: The monoclinic system requires use of the generation operators s and
s(5) via holohedral group \\2/m \\. Beginning with s(2), Sa transforms as
1 0 0 S11 S12 S31 1 0 0
S' s (2)S s (2)
0
0 1 0
0 1
S12 S22 S23 0
S31 S23 S33 0
1
0
0
1
S11 S12 S31
Sym.
S22 S23 .
S33
(3.11)
Applying Neumanns principle requires that S12 S23 0, giving the result
S11 0 S31
S
Sym. S2 0 ,
S33
(3.12)
where S22 S2 is a principal component along 0x2 0y. Application of operator s(5) leaves
the result of Eq. (3.12) unchanged. The same result could have been obtained with greater
ease by using the direct inspection method. For example, the use of generating matrix s(2)
in Table 3.5 gives
x1 x 1
1 1
(2)
s x2 x 2
x3 x 3
or
32
2
3
(3.13)
It now follows that components having a single 1 or single 3 subscript (but not both) must
be zero in accordance with Neumanns principle, that is, S23 S12 0 (all others must re
main nonzero), which is applicable to the three classes of the monoclinic crystal system.
3. Orthorhombic system: The holohedral group \\mmm \\ has the generation matrices s(4), s(5),
and s(6), which cover all classes of the orthorhombic system. From Table 3.5, these three
operators are given by
1 1 1 1 1 1
s(4) 2
s(5) 2
(6)
2 2 s 2 2 .
3 3
3 3 3
3
(3.14)
Taken separately and using the direct inspection method together with Neumanns princi
ple, the generation matrices s(4), s(5), and s(6) require all components having a single 1, a single
54 TENSOR PROPERTIES OF SOLIDS
2, or a single 3 be zero. Thus, S23 S31 S12 0, with all others being nonzero. Therefore,
S is now represented by
S11 0 0 S1 0 0
S 0
0
S22
0
0
S33
Sym.
S2 0 .
S3
(3.15)
The arrays in Eq. (3.15) apply to all crystal classes of the orthorhombic system. The second
rank property components S1, S2, and S3 are the principal components along the crystal
lographic axes 0x [100], 0y [010], and 0z [001], respectively.
4. Tetragonal system: The holohedral group \\4 /mmm \\ has the generating matrices s(4), s(6),
and s(9), of which s(4) and s(6) have previously been used for the orthorhombic crystal system,
and operator s(5) leaves these results unchanged. Then, applying the operator s(9) from Ta
ble 3.5 to the results of the orthorhombic system requires, by the direct inspection method,
that
x 2
x1 1 2
(9)
s x2 x 1 or 2 1 .
x3 x 3 3
3
(3.16)
The results are S31 S32
S31 0 and S11 S22 S1 in accord with Neumanns prin
ciple. This means that the property tensor Sij is everywhere isotropic in the x,y (001)
plane. Thus, the components of Sij for all point groups of the tetragonal crystal system are
represented by the array
S1 0 0
S
Sym. S1 0 .
S3
(3.17)
5. Trigonal and hexagonal systems: The holohedral groups \\3m \\ and \\6 /mmm \\ contain gen
erating operators s(1), s(3), s(4), s(6), and s(7). The application of the operators s(1), s(3), s(4), and
s(6) to the tensor Sij will leave unchanged the results obtained for the tetragonal systems.
Therefore, there remains only the application of the operator s(7). Because the method of
direct inspection is not applicable here, we must perform the transformation given by
But this transformation can be given more conveniently by using the quadratic transformation
1/4
3/4
3/4
1/4
0
0
0
0
0
0
3/2 S1
3/2 S2
S1
S1
S
(7)S
0
0
0
0
0
0
3/4 3/4
1 0 0
0 1/2 3/2
0 3/2 1/2
0 0 0
0 S3
0 0
0 0
1/2 0
S3
0
0
0
.
(3.19)
This indicates that the components of Sij for all point groups of the trigonal and hexagonal
crystal systems are the same as those for the tetragonal system. Consequently, these three
systems may be treated as a single group with respect to symmetrical secondrank tensor
properties. They are often called the optically uniaxial crystal systems.
6. Cubic system: The holohedral group \\m3m \\ contains generation operators s(4), s(9), and s(10),
all but s(10), of which have been applied to the previous, less symmetrical systems. So there
now remains the application of the generation operator s(10), to the results obtained for the
tetragonal, trigonal, and hexagonal systems. The method of direct inspection, which is
again applicable, requires that
x1 x2 1 2
32
(10)
s x2 x3 or 3 .
x3 x1 1
(3.20)
S1 S2 S3 S, (3.21)
meaning that any cubic crystal system is isotropic with respect to any symmetrical secondrank
property tensor.
To summarize, the effect of crystal symmetry on properties that are represented by sym
metrical secondrank tensors is given in Table 3.7. The effect of crystal symmetry on other tensor
properties will be given at the time the individual properties are considered. This is especially desir
able for the property tensors of higher rank because they often possess unique inherent symmetry.
This is particularly true for the axial and axialmagnetic property tensors for which both axial and
magnetic symmetry must be considered.
56 TENSOR PROPERTIES OF SOLIDS
HOLOHEDRAL INDEPENDENT
GENERATING COMPONENTS OF THE
SYSTEM MATRICES PROPERTY MATRIX
Triclinic s (1) S11 S12 S31
Sym.
S22 S23
S33
Monoclinic s (2), s (5) S 11 0 S31
Sym.
S2 0
S33
Orthorhombic s (4), s (5), s (6) S1 0 0
Sym.
S2 0
S3
Tetragonal, trigonal, s (1), s (3), s (4), s (6), s (7), s (9) S1 0 0
and hexagonal
Sym.
S1 0
S3
Cubic s (4), s (9), s (10) S 0 0
Sym.
S
S
0
for polar tensors of odd rank
T T 0 .
for axial tensors of even rank
(3.22)
CRYSTAL SYSTEMS, SYMMETRY ELEMENTS, AND SYMMETRY TRANSFORMATIONS 57
Thus, all 11 of the centrosymmetrical crystal classes, those that contain a centerofsymmetry, will
be lacking in oddrank polar tensor properties and evenrank axial tensor properties. For example,
the piezoelectric tensor dikl , included in Eq. (2.54), is a polar thirdrank tensor property whose
property components vanish for any of the 11 centrosymmetrical (holohedral) classes designated by
\\X \\ in Tables 3.4 and 3.6. Another example is the pyroelectric coefcient dened by $Pi Pi $T,
where the three components of pi are null for any of the 11 centrosymmetrical crystal classes. All
axial and axialmagnetic tensor properties of even rank will be lacking property components for
any of the centrosymmetrical crystal classes. The 90 magnetic point groups come into play only for
magnetic and axialmagnetic tensor properties of odd rank, further reducing the number of existing
components over those required strictly by conventional symmetry arguments.
for convenience, the generalized transformation law for longitudinal and transverse effects becomes
l1 l2 l3 S11
S12 S31 l1
m1 n1
~
S' aSa m1 m2 m3
n1 n2 n3 Sym.
S22 S23 l2
S33 l3
m2
m3
n2 .
n3 (3.25)
Equation (3.25) is valid for any crystal system in which the property Sij is manifest. We will now
explore the effect of crystal symmetry on the longitudinal and transverse effects.
1. Triclinic system: For the triclinic system, no restrictions are placed on the orientation of the
reference axes. If the effect parameter p is sensed along the 0xa1 when the cause parameter q
is applied in that same direction, the longitudinal effect for the triclinic system is given by
58 TENSOR PROPERTIES OF SOLIDS
p'1
S11 S12
S31 l1
S'11 q l1
'1 l2 l3 .
Sym.
S22 S23 . l2
S33 l3
2 2 2
l1 S11 l2 S22 l3 S33 2l2 l3 S23 2l3 l1 S31 2l1l2 S12. (3.26)
Here, the longitudinal effect is simply the magnitude of S measured along some arbitrary
direction 0xa1.
Similarly, if p is sensed along 0xa1 when q is applied along 0xa2 , or vice versa, the transverse
effect given by
p'1 p'2
S11 S31 m1
S12
S'12 q q l1
'2 '1
l2 l3 .
Sym.
S23 . m2
S22
S33 m3
is also applicable to the triclinic crystal system. Thus, to measure all six independent com
ponents of Sij , six independent measurements must be made using either the longitudinal
effect or transverse effect or some suitable combination thereof. The six resulting equations
must then be solved simultaneously to obtain the six components.
2. Monoclinic system: Applied to the monoclinic crystal system, Eqs. (3.26) and (3.27) for
the triclinic system can be simplied to the extent that S23 S12 0, as indicated in Table
3.7. All other terms in thee expressions remain the same, with S22 S2 S[010] being the
principal component along 0x2 0y [010]. Four independent measurements, using either
the longitudinal or transverse effects or some combination of them, will yield four indepen
dent equations from which the four independent components of Sij can be obtained. Note
that the magnitude of the property Sa11 measured along the axis of symmetry 0x2 0y is the
principal component S2.
3. Orthorhombic system: The longitudinal and transverse effects can be put into special forms
for the orthorhombic crystal system when we note that S23 S31 S12 0 and that the prin
cipal axes lie along the crystallographic axes. The longitudinal effect now becomes
where l100 are the direction cosines between any direction 0xa1 [uvw] and the crystal
lographic (principal) axes, [100], [010], and [001], and S100 represent the three principal
CRYSTAL SYSTEMS, SYMMETRY ELEMENTS, AND SYMMETRY TRANSFORMATIONS 59
components along these axes. Similarly, if the direction 0xa2 [m1, m2, m3] is also taken
with respect to the crystallographic axes, the transverse effect for the orthorhombic crystal
system is given by
Thus, knowing the orientation of the principal axes, three independent measurements using
either the longitudinal effect or transverse effect or both, will yield the principal values S1, S2,
and S3.
4. Tetragonal, trigonal, and hexagonal systems: For the optically uniaxial crystal systems (te
tragonal, trigonal, and hexagonal) the longitudinal effect requires measurement of the two
independent components, S1 and S3, along any two arbitrary, but different, directions (one
direction must be out of the (001) or (0001) plane). Accordingly, the longitudinal effect is
established from Eq. (3.28) as
2 2 2
a p 1a / q 1a (l [100]
S 11 l [010])S[100] l [001] S[001]
2 2
(1
l [001])S[100] l [001]S[001] (3.30)
since now S[100] S[010] due to the isotrophy of property S in the (001) or (0001) plane for
the optically uniazial crystal systems.
Dening the Eulerian angles Q and F as shown in Figure 3.5, the longitudinal effect
takes the form
a S>sin2F S\\cos2 F
S 11 (3.31)
z = [001]
[uvw]
y = [010]
x = [100]
FIGURE 3.5: Arbitrary direction [uvw] expressed in terms of the Eulerian angles F and Q
60 TENSOR PROPERTIES OF SOLIDS
independent of Q. Here S> Suv 0 is the magnitude of the property along any direction
uv 0 perpendicular to the [001], and S\\ S[001] is the magnitude of the property parallel to
the [001] direction. Consequently, the magnitude of the property in any direction [uvw]
0xa1 depends only on the angle F and the values S> and S\\. For the trigonal and hexagonal
crystal systems, the longitudinal effect may be represented alternatively as
61
CHAPTER 4
dU dQ dW,
where dQ is the thermal energy (heat) transferred to the system and dW is the external work done
on the system. Here, dQ and dW are inexact differentials called Pfafansthey are pathdependent.
For a closed solidphase system, the innitesimal change in internal energy is given by the rst and
second laws of thermodynamics as
_ _ _ _ _ _
dU = d Q + i dWi = TdS + dW + dWMag.+ dWMech.+ dWChem.
Elect. (4.1)
in which dQ = TdS is the innitesimal reversible heat absorbed by the solidphase system at an
absolute temperature T, and dS is the innitesimal entropy change associated with the absorbed
heat dQ. 3dW is the sum of all innitesimal reversible work (electrical, magnetic, mechanical and
i i
TABLE 4.1: Intensive and extensive parameters for a solidstate system and their SI units
elastic strain energy Td (V0E) for the case of solids. Furthermore, the fact that solids can develop
a net polarization or magnetization adds additional complications to the energy representation
electrical and magnetic work terms must be added.
The intensive and extensive parameters that best describe the equilibrium tensor properties
of crystals are presented in Table 4.1 along with their SI units. Note that the magnetic intensive
parameter is the magnetic ux density B NH measured in the absence of the crystal system (N
is the permeability in a vacuum and H is the magnetic eld strength). Using these parameters, the
total innitesimal change in internal energy for a solidphase system is given by
dU T dS E dP B dI d ( V0 ) d N (4.2)
in agreement with the respective work terms given in Eq. (4.1). From Eulers theorem on homoge
neous rstorder forms, the corresponding Euler relation is given by
U T S EP BI ( V0 ) N . (4.3)
The Euler relation is a thermodynamic potential seen to combined rst and second laws of thermo
dynamics in terms of the product of conjugate parameters (in energy units of Joules, J ) given in
Table 4.1. The Euler relation will later be used in the generation of other useful thermodynamic
potentials for a closed solidphase system of one component (dN = 0).
Differentiating Eq. (4.3) gives the result
dU T dS S d T E d P P d E B dI I dB d ( V0 ) ( V0 ) d d N N d ,
GENERALIZED THERMOSTATICS AND CORRELATION OF PHYSICAL PROPERTIES 63
S d T P d E I dB ( V0 ) d N d 0 (4.4)
Equation (4.4) is the general form of GibbsDuhem equation for a solidphase system of a single
component (d N 0).
The concepts of equilibrium and spontaneous (irreversible) processes are best understood in
terms of the thermodynamic potentials G and F called the Gibbs and Helmholtz free energies, respec
tively. The extended Gibbs free energy for a single component solidphase system is dened as
G N U TS E P BI ( V0 ), (4.5)
which follows from the Euler relation. This potential is the Legendre transform of U that simulta
neously replaces S by T, P by E, I by B and EV0 by S as the independent variables. Differentiating
Eq. (4.5) for a closed solidphase system of one component and introducing Eq. (4.2) gives the
innitesimal change in Gibbs free energy
dG S dT P d E I d B ( V0 ) d (4.6)
In actual experimental situations, it is often a simple matter to hold the intensive parameters
constant. When this is done, that is, when T, E, B, and S are held xed, the solidphase system is
said to be thermally, electrically, magnetically and mechanically free resulting in
dG = 0 (4.7)
as the criterion for thermodynamic equilibrium. When one or more of the intensive parameters are
varied, then
dG < 0 , (4.8)
and the process is said to be spontaneous or irreversible. Clearly, the condition dG applies to a
process that will not take place without changing the thermodynamic parameters of the system.
The Helmholtz free energy is a thermodynamic potential dened as
F U TS . (4.9)
Thus, the Helmholtz free energy is the Legendre transform that replaces the entropy S by tempera
ture T as the independent variable. Differentiating Eq. (4.9) for a closed solidphase system of one
component and introducing Eq. (4.2) gives the innitesimal change in the Helmholtz free energy as
d F S dT E d P Bd I d( V0 ) (4.10)
64 TENSOR PROPERTIES OF SOLIDS
which eliminates the difcult task of holding entropy constant to establish equilibrium but retains
the extensive parameters P, I, and EV0 as the independent variables. Thus, in experimental situa
tions when T, P, I, and EV0 are held constant, the system is said to be thermally free but electrically,
magnetically, and mechanically, clamped. Under these conditions,
dF = 0 (4.11)
as the criterion for thermodynamic equilibrium. It also follows that d F 0 corresponds to an irre
versible or spontaneous thermally free process at constant P, I, and E, whereas d F 0 corresponds,
to a spontaneous isothermal but electrical, magnetic and mechanical clamped process. Other ther
modynamic potentials may also serve usefully as criteria for thermodynamic equilibrium under the
appropriate clamped and/or free conditions.
d u dU / V0 T ds E d P B d M d (4.12)
and
d g dG / V0 s d T P d E M d B d , (4.13)
TABLE 4.2: The 16 thermodynamic potential densities and their differentials for a closed solid
state system of one component
and S which is analogous to CP in the classical sense. Still other potentials, such as F, F, F, and
including F are useful in developing Maxwells relations for the dependent coupled effects holding
certain intensive parameters constant. The reader will note that the differential forms dFi result by
differentiating Fi followed by introduction of Eq. (4.12), du = T d s + E d P + B d M + SdEto com
plete the Legendre transform of u. For example, differentiating F13u EP gives
d 13 d u E d P P d E T d s E d P B d M d E d P P d E
Td s P d E B d M d
u u u u
du
d s
dPi
d Mi
dij
s P,M,
u
T The absolute temperature (4.15)
s P,M,
u
Ei The external electric eld strength vector (4.16)
P
i s,M,
u
Bi The external magnetic ux density vector (4.17)
M i s,P,
u
ij The stress tensor. (4.18)
ij
s,P,M
In these denitions, T is a scalar and is specied by one component, Ei and Bi are vectors each speci
ed by three components (Bi is axial magnetic in character), and Sij is usually a symmetrical second
rank polar tensor (Sij Sji ) specied by six components as in Eqs. (2.17) and (2.20).
Now, let the letter I represent the intensive parameters (T, Ei , Bi , Sij ) and the letter e repre
sent the extensive parameters (s, Pi , Mi , Eij ) so that an innitesimal change in the internal energy
density is given in the compact form
d u = Im d em (m = 113). (4.19)
has been written in the form ( I1 d e1 + I2 d e2 + ... + I13 d e13 ), where the stress and strain compo
nents have been unfolded according to the matrix scheme of Eq. (2.20) for symmetric secondrank
tensors.
In a similar manner, the extensive tensor parameters can be dened by using the general
ized Gibbs free energy density. For any closed solidphase system of one component, the fun
damental equation of state becomes g g (T, Ei , Bi , Sij ), and we write for the rst differential
of g
g g g g
dg
dT
d Ei
d Bi
dij
Again, by comparing coefcients there results the following denitions for the extensive parameters
of a closed system holding certain intensive parameters constant:
g
s The entropy density (4.21)
T
E,B,
g
Pi The total electric dipole moment per unit volume
Ei
T,B, or (polarization) (4.22)
g
g
ij The strain tensor. (4.24)
ij T, E, B
As with their conjugate intensive parameters, s is a scalar, Pi and Mi are vectors of three components
each (Mi is axial magnetic in character), and Eij is usually represented as a symmetrical secondrank
tensor (Eij = Eji ) specied by six components as in Eq. (2.20).
An innitesimal change in the Gibbs free energy density may also be represented in the
compact form
68 TENSOR PROPERTIES OF SOLIDS
dg = em dIm (m = 1 13),
(4.25)
where (e1 dI1 + e2 dI2 + ... + e13 dI13) represents the sequence
( s d T P1 d E 1 P2 d E 2 P3 d E 3 M1 d B1 M 2 d B 2 M 3 d B 3 1d 1 2 d 2 ... 6 d 6 ).
Here again, the stress and strain components have been unfolded according to the scheme given by
Eq. (2.20).
s s (T , Ek ,Bk , kl );
Mi Mi (T , Ek , Bk , kl )
ij ij (T ,Ek,Bk , kl ).
(4.27)
Carrying out these Taylor series expansions and accepting only the rstorder terms (n 1),
thus neglecting the second and higherorder differential terms, the innitesimal changes in the
extensive parameters are given by the linear rstorder equations:
s
s
s
s
ds dT dEk dBk dkl
T E,B,
Ek
Bk
kl T,E,B
T,B, T,E,
P
P
P
Pi
dPi i dT i dEk i dBk dkl
T
Ek T,B,
Bk T,E,
kl T,E,B
E,B,
Mi
Mi
Mi
Mi
d Mi dT dEk d Bk d kl
T E
k T,B, Bk kl T,E,B
E,B, T,E,
The partial derivatives are called the property compliances, where the subscripts indicate
those intensive parameters that are held constant. Now, we designate the property compliances
by the letter C with the appropriate subscripts and superscripts, such that (us / uT )E,B,S C s,T,
(us /uEk )T,B,SCks,E, etc., thereby permitting us to set Eqs. (4.28) in the matrix form given by Eq. (4.29).
This matrix equation is called the general property compliance matrix for rstorder equilibrium prop
erties. The tensor rank of any compliance is indicated by the number of subscripts it has. Thus, it is
ES
seen that the tensor rank varies from zero for C s,T to rank 4 for the compliance Cijkl .
ds C
s,T
Cks,E Cks,B Ckls, dT
dP
C P,T CiP,E CikP,B CiP,
i
i k kl
dEk
dMi
C M,T
( i, j , k , l 1 3 )
CiM,E CiM,B CiM, dBk
i ,T k k kl
ij
Cij
d Cijk,E Cijk,B Cijkl,
dkl
(4.29)
A close inspection of the compliance matrix (4.29) reveals that it is, in reality, a (13 x 13)
matrix of tensor components if stress and strain are taken as symmetrical secondrank tensors. This
is illustrated in Table 4.3 where the individual property matrices are designated by (r s c), meaning
rows by columns. The four principal effects of the property compliance matrix lie along its leading
diagonal and are shaded. The offdiagonal compliances represent the coupled (interaction) effects.
If we let e represent the extensive parameter components and I represent the intensive pa
rameter components, then the set of linear rstorder equations for the compliances in Table 4.3 are
expressed in contracted subscript form as
C29 CP1, 2 (P1 / 2 )T,E,B, , ,
1 3 6
C46 CP3, B2 ( P3 / B2 )T, E, B
1 ,B2 ,
C13,13C6, 6 ( 6 / 6 )T,E,B,
(4.31)
70 TENSOR PROPERTIES OF SOLIDS
TABLE 4.3: Component arrangement of the general compliance matrix emphasizing the principal
effects along the leading diagonal (shaded regions), all other being the coupled effects
n 1 2 3 4 5 6 7 8 9 10 11 12 13
m T E 1 E2 E3 B1 B2 B3 1 2 3 4 5 6
1 s C s,T (0) C s,E (1 3) C s,B (1 3) C s, (1 6)
2 P1
3 P2 C P,T (3 1) C P,E (3 3) C P,B (3 3) C P, (3 6)
4 P3
5 M1
6 M2 C M,T (3 1) C M,E (3 3) C M,B (3 3) C M, (3 6)
7 M3
8 1
9 2
10 3 C ,T (6 1) C ,E (6 3) C ,B (6 3) C , (6 6)
11 4
12 5
13 6
Thus, a given compliance is a quantity that expresses the rate of change of one particular extensive
property component with respect to an intensive property component holding all other intensive
parameter components constant.
Following the same procedure, the intensive parametric equations of state are
T T (s ,P,M , )
E E (s , P, M , )
B B (s ,P ,M , )
(s ,P , M , ) (4.32)
From these, there results the following linear rstorder equations expressing the innitesimal
changes in intensive parameters as functions of innitesimal changes in the extensive parameters:
GENERALIZED THERMOSTATICS AND CORRELATION OF PHYSICAL PROPERTIES 71
T,s
dT R RkT,P RkT,M RT,k ds
dE RE,s RiE,P RiE,M
REikl, dP
i i
k k k
( i, j , k , l 1 3 )
dBi RB,s RiE,P RikB,M RiB,kl dMk
i
k
d ij
Rij s Ri,P Rijk Rij,kl
d kl
(4.33)
jk
Here, the R matrix is called the general property rigidity matrix for the rstorder equilibrium tensor
properties. Equations (4.33) can be represented in contracted tensor subscript form as
where it follows that the rigidity and compliance matrices have an inverse relationship given by
R = C 1. (4.35)
R46 RE3,M2 ( E3 / M2)s,P,M
,M ,
R13,13 R , (6 / 6 )s, P, M,
.
(4.36)
In the above developments, only innitesimal reversible changes in the intensive and exten
sive parameters were considered, and all solidphase systems were assumed closed on their bound
aries. Furthermore, we have suppressed the names of the various property compliances and rigidities
until symmetry considerations have been discussed in the next section. Let it sufce for now to say
that the properties along the leading diagonals of the general compliance and rigidity matrices each
represent four principal effects, whereas the offdiagonal symbols represent the 12 interaction effects
often called coupled effects.
state of the solid. A thermodynamic property is, therefore, any quantity that depends on the state
of the solid and that is independent of the path taken to reach that state. Such quantities are called
state functions and form exact differentials. For the intensive and extensive parameters that are eld
tensors of rank 1 or 2 (T and s are scalars), the term thermodynamic property refers to an individual
component of the tensor. For example, F = g in Table 4.2 represents the Gibbs free energy density
g(T ,E ,B , S) g(T ,E1 ,E2,E3 ,B1 ,B2 ,B3 , S1, S2,S3) in which g is given as function of 13 thermo
dynamic properties (intensive parameter components). Thus, it follows that although g is intensive
in nature, internal energy density u is extensive in nature and all other Fi in Table 4.2 are of mixed
character.
Consider any thermodynamic property Z( p,q) of a solid that is a function of any other two
thermodynamic properties, p and q. Now suppose that the substance is taken from its initial ther
modynamic state through a series of states allowing p and q to vary independently in some arbi
trary manner and that the process may be either reversible or irreversible. Finally, if the substance
is returned to its initial state, we would notice that $Z since Z depends only on the initial and
nal states, which, in this case, are the same. The independence of path of a given thermodynamic
property Z is expressed mathematically by Greens theorem in a plane (special case of Stokes theo
rem) given by
( p, q )
C
p
d p
q
d q
M N
C
(M d p N d q )
S
d p d q 0
q p p q
(4.37)
for any simple closed path C in a given region Ra. It follows, therefore, that
N 2 2 M
p p q q p q (4.38)
if M( p,q) and N( p,q) have continuous derivatives in region Ra. Simply stated, the order of differ
entiation of any thermodynamic property Z is immaterial. This result is essential in describing the
symmetry of the generalized compliance and rigidity matrices from which come the Maxwell rela
tions. It will also be most useful when discussing the symmetry of second and higherorder tensor
properties in subsequent chapters.
We now apply Eq. (4.38) to the extended Gibbs free energy density. From Eq. (4.25) for any
component, em of an extensive parameter is dened by
g
em = .
Im (4.39)
GENERALIZED THERMOSTATICS AND CORRELATION OF PHYSICAL PROPERTIES 73
em
Cmn = .
In (4.40)
Because the order of differentiation is immaterial, we have the important result that
em 2 g 2 g e
= = = n (4.41)
In In Im Im In In
or
The meaning of Eq. (4.41) is straightforward. With reference to Table 4.3, only the principle
effects (those along the diagonal and shaded) possesses selfsymmetry expressed by
~ ~ ~
CP,E = CP,E, CM,B = CM,B, C = C ,
meaning that the principle property compliance matrices (of components) taken separately are equal
to their transpose. All other (coupled) property compliance matrices are related to the correspond
ing ones across the leading diagonal according to the Maxwell relations given later in Section 4.5.2.
^ ^ ^ ^
For example, while C P,B C M,E, it also follows that C P,B x C P,B and C M,E x C M,E ; or while C P,S C E,E,
^ ^
it is clear that C P,S x C P,S or C E,E x C E,E. Consequently, the 13 s 13 compliance component matrix
shown in Table 4.3 is symmetric, about the leading diagonal (within the shaded regions), which
reduces the number of independent compliance components from 169 to 91. This type of inherent
symmetry is called thermodynamic tensor symmetry since it arises from thermodynamic arguments. It
must be remembered that the symmetry expressed by Cmn Cnm applies only to the tensor compo
nents on the leading diagonal of the generalized compliance matrix.
By similar reasoning, it follows from Eq. (4.19) that
u ,
Im =
en (4.42)
where an innitesimal change in any intensive parameter is given by dIm = Rm en. Again applying
Greens theorem in a plane yields the result
Im 2u 2u I
= = = n
en en em em en em (4.43)
74 TENSOR PROPERTIES OF SOLIDS
or
We note that this result could have been deduced from Eq. (4.35). Consequently, the 13 s 13 rigid
ity component matrix is also symmetric about its leading diagonal thereby reducing the number of
independent rigidity components from 169 to 91.
It must be understood that the socalled thermodynamic tensor symmetry is in no way associ
ated with the symmetry of the crystal in which the tensor properties may or may not be manifest.
Thus, the symmetry expressed by Cmn Cnm and Rmn Rnm applies generally to all crystal systems.
Operation of the minimum generating matrices given in Table 3.6 and the application of Neumanns
principle given in Section 3.6 for symmetric secondrank tensors may result in a reduction of inde
pendent components required to specify the property for that point group. This will be done sepa
rately and selectively for the tensor properties as they are discussed in later developments.
s
TC s,T T
C E, B, , specic heat (Heat capacity per unit volume) (4.44)
T E, B,
Pi
1
0
CiP,
k
E
1
0
ik T , B, , dielectric susceptibility tensor (4.45)
E
k T, B,
Mi
0CiM,B
k
0
k T , E,
i
, magnetic susceptibility tensor (4.46)
Bk T , E,
Ci
jkl
By application of the results of the previous section, we nd these principal effects have the
following thermodynamic tensor symmetry:
~
ik ki
( i , k = 1, 2 ,3 ) or (4.48)
~
ik ki ( i , k = 1, 2 ,3 ) or (4.49)
It follows, therefore, that the two susceptibilities are symmetrical secondrank tensors, whereas the
fourthrank elastic compliance tensor sijkl is symmetric with respect to the interchange of pairs (ij )
and (kl ). It will later be shown that Sij and Eij are nearly always symmetrical secondrank tensors.
s P
1
p1
B,
E 1 T , E ,E T E,B,
2 3,B,
s P
3
p3
B,
E
3 T , E 1 ,E T E,B, (4.51)
2,B,
76 TENSOR PROPERTIES OF SOLIDS
These equations state that the electrocaloric coefcients are numerically equal to the corresponding
pyroelectric coefcients, and both are represented by the rstrank polar tensor pk (k 1,2,3). Thus,
Eqs.(4.51) derive from dg
sdt
PdE
MdB
EdS to which we apply Stokes theorem to give
2g / T E B,
2 g / E T or ( / E)( g / T ) ( / T )( g / E )B,
where ug/uT
s and ug/uE
P, thereby yielding Eqs. (4.51) at constant B and S.
2. Pyromagnetic Effect
s M
1
q1 E,
B
1 T ,E , B2 ,B3, T E,B,
s M
3
q3 E,
These equations state that the magnetocaloric coefcients are numerically equal to the corresponding
pyromagnetic coefcients, and both are represented by the rstrank tensor qk (k 1,2,3), which is both
axial and magnetic in tensor character.
3. Thermal Expansion
s 11
= = ( 11)
11 T ,E, B, T E ,B, E,B
22 12
s 12
= = ( 12 )
12 T ,E, B,
T E , B , E, B
(4.55)
11 31
which states that the piezocaloric coefcients are numerically equal to the corresponding thermal
expansion coefcients and that both are represented by the secondrank polar tensor Aik(i,k ).
It is assumed that stress, strain and thermal expansion are all symmetric secondrank tensors that
are unfolded according to the schemes of Eqs. (2.19) or (2.20).
4. Magnetoelectric susceptibility
P 1
M 1
11
B1 T, E, B2, B3,
E 1 T, E, B2, B3,
T,
P 2
M 1
21
T,
B1 T , E, B E 2 T, E ,E , B,
(4.57)
2 B3
, ,
1 3
Here, the corresponding coefcients of the direct and converse magnetoelectric susceptibility effects are
numerically equal and are represented by the asymmetrical secondrank tensor Lik which is axial and
magnetic in character. Note that the components have been unfolded according to the following
schemes:
Tensor notation: S11 S22 S33 S23 S31 S12 S32 S13 S21 (4.59)
5. Piezoelectric Effect
P1 11
d111
11
T ,E, B,
E1
T,E T ,B
22 12 2,E3,B,
P3 12
d312
E T ,B
12
T ,E, B,
3
T, E , E (4.61)
11 31 1 2 ,B,
~
C P)T,E,B = C ,E )T ,B, = (d )T ,B . (4.62)
78 TENSOR PROPERTIES OF SOLIDS
These equations state that the corresponding 18 components of the direct and converse piezoelectric
effects are numerically equal and are represented by the thirdrank polar tensor dijkl in the form of Tim
given by Eq. (2.30) where the partial inherent symmetry is expressed by dikl dilk dim.
6. Piezomagnetic Effect
M1 11
Q111
B T ,E
11
T ,E, B,
1
T, E,B ,B ,
2212 2 3
M3 12
Q312
12
T , E, B,
B3
T, E,B ,B , T ,E
(4.63)
11 31 1 2
~
C M)T, E,B = C ,B )T , E , = (Q)T , E . (4.64)
Similar to the piezoelectric effects, the corresponding 18 components of the direct and con
verse piezomagnetic effects are numerically equal. They are represented by the axialmagnetic
thirdrank tensor with the partial inherent symmetry Qikl Qilk Qim, assuming that stress and
strain are symmetric secondrank tensors and are expressed by a tensor of the form given by
Eq. (2.30).
Thus, of the 16 properties represented by the general compliance matrix, only 10 are inde
pendent, 4 principal and 6 coupled effects. The same is true for the general rigidity matrix. It will be
left as and exercise for the reader to repeat the above correlation procedure for the rigidities.
converting property coefcients in the clamped state to those in the free state or vice versa is one,
which we shall now consider.
Let a clamped compliance be that compliance that is measured holding any one of the ex
tensive parameters (s,P,M, or E) constant. Also, let a free compliance be one that is measured hold
ing any one of the intensive parameters (T,E,B, or S) constant. Now, consider any two extensive
parameters a a(A , B) and b b(A , B) that are functions of any two intensive parameters A and B.
From the equations dem Cmn dIn, we write
a a
da
d
d
(4.65)
and
b
b
db d d
(4.66)
b b
0 d d
b
b
b
giving the result
b
d d
b (4.67)
a
a
b
da d d
b (4.68)
a a a b
b
b
or
in symbolic notation. Equation (4.69) gives the difference between the clamped (C a, A)b and free
(C a, A)B compliances and requires that all other intensive parameters G,D, and so forth be held con
stant and that b and B be conjugate parameters.
Application of Eq. (4.69) is simply accomplished by selecting the desired compliance through
choice of a and A and the clamped and free conditions through choice of the conjugate parameters
b and B. For example, the difference between the mechanically clamped and free heat capacities is
obtained by the following choice of parameters
a s T
(E, B constant)
b
s s s ij kl
,
(4.70)
T
T ij T kl T T
where E and B are assumed to be held constant. But (us / uSij)T = (uEij / uT )S = Aj by Maxwells rela
tion and (uSij/uEkl )T (cijkl )T where (cijkl )T is the isothermal elastic stiffness coefcient. From this, we
nd the difference between the mechanically clamped and free heat capacities to be
C C T ij c ij k l k l ( i , j , k , l 1 3)
C C T i c ij j T ~ c (i, j 1 6 ) (4.71)
T T
a P E
(B constant),
b s T
Pi Pi
Pi T s ,
E E T E s E Ej (4.72)
j s j T T
GENERALIZED THERMOSTATICS AND CORRELATION OF PHYSICAL PROPERTIES 81
where B and S are held constant. However, because (uPi / uT )E (us / Ei)T pi from Maxwells rela
tions, there results
T
( ) ( ) = pi pj ( i , j = 1 3 ), (4.73)
ij s ij T 0 CE
where T (us / T )E CE with B and S held constant, and pi pj is the dyadic or outer product of the
pyroelectric coefcients.
The above two examples demonstrate how one could obtain the difference between clamped
and free principal effects. However, the difference between clamped and free coupled effects can be
obtained with equal ease. As a third example, suppose it is desired to know the difference between
the electrically clamped and electrically free coefcients of thermal expansion. For this purpose, the
choice of parameters must be
a T
b P E
(B constant),
ij E k P m
ij ij
T E P T . (4.74)
P T
E k
T m
T
E
But according to Maxwells relations, (uEij/ uEk)T (uPk/uSij )E dkij , with the result that
or
~
P E 01 dT 1T, p
TABLE 4.4: Differences between clamped and free rstorder property compliances given in
conformable matrix order for the principal and coupled effects.
(1) C P C E 0 T ~
p ( T ) 1 p (13) Q s QT (T / C B , )q ~ BE
B ,
(2)
~ ( ) 1 q
C M C B 01T q T
E, (14) QP QE 0 1 ( B , ) 1 d B T
~ c
C C T p EB
ds d T (T / C E , ) p ~
(3) T E, B (15)
(4) p B ,
T (T / 0 ) C E p ~ (16) dM d B 0 ( E , ) 1 QE
s T
~
(5) 1 ~
M E ( 0 / 0 ) ( E ) T,
(17) P E 0 1 d T ( T , ) 1 p
B
~
(6)
1
o dcE d T, B (18)
~
M B 0 QT ( T ,) 1 q E
~
(7) s T ( 0 T / C B ) q q~E , (19) qP q E 01T ( T , B ) 1 p B
(8)
~ 1
P E ( 0 / 0 ) ( B ) T,
(20) q q Q T cT , B B
E
~
(9) 0 Q cB Q T , E (21) pM p B 0 T ( T , E )
1
qE
~ *
(10) ss sT (T / C ) E,B (22) p p dT c T , E E B
~
(11) sP sE 0 1 d ( ) 1 dT , B (23) s T (T / C E , B) p B q~ E
~ ~
(12) s M sB 0 Q ( ) 1 Q
T, E (24) d B c E, B QE T
* Difference between the isentropic (constant entropy density) and isothermal elastic compliances.
GENERALIZED THERMOSTATICS AND CORRELATION OF PHYSICAL PROPERTIES 83
Table 4.4 in conformable matrix order. To use the table, one only needs to replace the symbols by
their respective matrices and carry out the multiplication as indicated. The tilde appearing above
some of the symbols indicates the transpose of the normal matrix form. This may be illustrated by
expanding Eq. (4.75), which is Eq. (17) in Table 4.4 (all at constant B), as follows:
Keep in mind that crystal symmetry considerations can greatly reduce the number of property com
ponents needed for use in equations of the type just given and, as a consequence, greatly reduce the
matrix calculation time and effort to obtain a result.
The matrix equations in Table 4.4 may be used to obtain orderofmagnitude values for the
differences between clamped and free compliances. However, in using any one equation, great care
must be exercised in choosing representative magnitudes of the properties. Remember that the val
ues of the components usually differ somewhat within each tensor and that these magnitudes my
vary dramatically from crystal to crystal if, in fact, they exist at all by reason of normal crystal and
magnetic symmetry.
It can be easily veried that the inverse of Eq. (4.69) is
R , a R , a b R , b b C , b b R , b (4.77)
giving the difference between free and clamped rigidity coefcients. In the case of rigidities, it is
required that all other extensive parameters c, d, , and so forth. be held constant and that b and B
be conjugate parameters. This also leads to 24 equations of the type shown in Table 4.4.
85
CHAPTER 5
The independent principal and coupled rstorder effects are featured in Table 4.3, which gives
the component arrangement of the general compliance matrix. The four principal effects are those
relating the conjugate parameters along the leading diagonal (the shaded regions) and possess
thermodynamic selfsymmetry. The six coupled effects are the offdiagonal regions in Table 4.3
and relate intensive parameters to nonconjugate extensive parametersthe opposite being true
for the general rigidity matrix. Consequently, offdiagonal effects exhibit no selfsymmetry. How
ever, they do possess thermodynamic tensor symmetry expressed by the six Maxwell relations in
Section 4.5.2 and by Eqs. (4.41a) and (4.43a). For this reason, they are labeled independent
coupled effects.
2 7 2 7 7
7
T T
or T
T
,
P ,B P ,B
86 TENSOR PROPERTIES OF SOLIDS
s
ij
ij
T
t ij P ,B
T,P ,B P ,B,
There are many other examples of dependent coupled effects. In fact, an examination of
Table 4.2 will indicate that there are four sets of clamped and/or free conditions for each of the
six dependent coupled effects and their inverse, leading to a total of 48 equations of the type ex
emplied above. Thus, the choice of the thermodynamic potential used to obtain a given Maxwell
relation will depend not only on the particular coupled effect involved but on what parameters are
desired to be held constant.
For the sake of illustration here, let us require that all effects be dened in such a way that only
the intensive parameters are held constant. By using just four thermodynamic potentials F2, F3, F4,
and F5, the following six Maxwell relations, representing the six additional coupled effects, are given
in the order of increasing tensor rank.
Pi
T
hi
s Ei B, (from F5) (5.1)
E,B, s ,B,
s B
M
i
i
T
E, (from F3) (5.2)
i T ,E, E ,M,
s
ij
ij
T
t ij
E,B (from F2) (5.3)
T,E,B E,B,
Mj E
P
i
Bj
ij T , (from F4) (5.4)
i T ,B, T ,P ,
jk
Ei
P
jk
ijk
T ,B (from F4) (5.5)
i T ,B, T,P ,B
jk Bi
M
jk
mijk
T,E
(from F3) (5.6)
i T ,E, T,E,M
The inverse of each of the above relations is readily obtained from a different thermodynamic po
tential chosen from the same group F2, F3, F4, and F5. For example, (hi1)B,S results from F4.
DEPENDENT COUPLED EFFECTS 87
T T s T
or hi
pi
(5.7)
Ei s Ei B, B, C B,
giving an additional expression for the dependant pyroelectric effect vector, all at constant B and S.
But it is easily veried that three other interaction diagrams shown in Figure 5.2 can also be
used to describe hi , leading to the three additional equations that follow, all at constant B and S.
Similarly, the interaction diagram shown in Figure 5.3 represents the Maxwell relation in
Eq. (5.4) for the dependent coupled effect Nij = (uEi / uBj)P. From this diagram, there results the
equation
j p1 q
i j T , (5.9)
i
ij 1 1
1
0 ik kj 0
1 d i1kl Qklj
ik kj
(5.10)
T/C
T s
h
p
FIGURE 5.1: Interaction diagram for dependent coupled effect h in Eq. (5.1) at constant B and S.
88 TENSOR PROPERTIES OF SOLIDS
T T T
p1
h h q1 h
1
E P E E
0
M
d
FIGURE 5.2: Additional interaction diagrams representing the dependent coupled effect h in Eq (5.1),
all at constant B and S.
Following the same procedure, the four expressions for each of the remaining four dependent
coupled effects are readily obtained. These, together with those illustrated previously, are given by
the following six sets of equations all given in conformable matrix order:
~
h T /C p 0 p1 q1 d 1 (B,S constant) (5.11)
C / T q1 1 p 0 1 q Q1 (E,S constant) (5.12)
~ ~
t C / T 1 d 1 p Q1 q s1 (E, B constant) (5.13)
~
p1 q~ 01 1 01 1 d 1 Q (T,S constant) (5.14)
p1 s
E
q
FIGURE 5.3: Interaction diagram for dependent coupled effect U in Eq. (5.4) at constant T and S.
DEPENDENT COUPLED EFFECTS 89
( 0)1
E P E E
1
d 1
B B M B
/ 0
Q
FIGURE 5.4: Additional interaction diagrams representing the dependent coupled effect U in Eq (5.4),
all at constant T and S.
the property symbols indicates the transpose of the normal matrix form of the tensor. The normal ma
trix dimensions (rows scolumns) for rst and thirdrank tensors are (3 s1) and (3 s6), respectively.
The normal matrix dimensions for a secondrank tensor property are either (3 s3) or (6 s1), the latter
being the column form of symmetrical secondrank tensor properties such as A, C and Y, all of which
are polar in character. As dened by Eqs. (4.57) in Section 4.5, the magnetoelectric susceptibility L
is an asymmetrical axialmagnetic secondrank tensor and has normal matrix dimensions of (3 s3).
However, unfolded according to arrays given by Eqs. (4.59) and (4.60), it would be represented as a
(9 s1) column matrix with axial character. Because the properties q, L, and Q are axialmagnetic (rst,
second, and thirdrank tensors, respectively), the dependent coupled effects H N, and m are also
axialmagnetic in tensor character. The three remaining dependent coupled effects are polar tensors.
The six sets of equations, Eqs. (5.11) to (5.16), have some important uses. First they can be
used to obtain the components for any dependent coupled tensor property from known components
of the more common rstorder properties dened in Section 4.5. As an example, suppose it is desired
to know the six components of the isometric thermal stress coefcient tij given by Eqs. (5.13) and de
termined at constant E and B elds subjected to a particular crystal. If the heat capacity CSand coef
cients for thermal expansion Aij are known for the crystal, as they commonly are, or if the piezoelectric
moduli d and the pyroelectric coefcients p are known, then Eqs. (5.13) give two alternatives for the
determination of tij at constant E and B.
t1 1
1
d 111
1
d 12 1
d 13
t 1 1 1
2
2 21 d d 1 d 23
22
p
t C 1 d 1 1
d 1 1
33 p
d 32
3
13
= 1
31
1 1 2
t 4 T 4 d 41 d 42 d 43 p
t 1 d 1 1 1 3
d 52 d 53
5 15 51
t 6 1
6 d 61 1
d 62 d 1
63
(5.17)
90 TENSOR PROPERTIES OF SOLIDS
^
Here, it should be understood that quantities such as d 1 represent the component inverse (recipro
cal) of its transpose, a twostage operation from the normal (3 s6) form.
There are many other such examples, including the inverse of the six dependent coupled ef
fects given by Eqs. (5.11)(5.16). For example, with reference to Eq. (5.3), the components of the
effect (uTi / uSij)s , which describes the adiabatic application of stress, can be obtained by taking the
inverse of Eq. (5.17) to give (uTi / uSij)s = (T / CS)Aij all at constant E and B. These same results can
also be obtained from the application of Stokes theorem to the generalized enthalpy, F5 = h given in
Table 4.2, followed by the appropriate interaction diagram.
Another important use of the six sets of equations, Eqs. (5.11)(5.16), is to interrelate the
various rstorder effects. Suppose, as a typical example, it is desired to nd the components of the
magnetoelectric susceptibility L for a particular crystal under conditions of constant T and S. If
the components of the dielectric susceptibility C, those of the piezoelectric coefcient d, and those of
the piezomagnetic coefcient Q are all known for a particular crystal, Eqs. (5.14) yield the result
~ (5.18)
1
0
1 d 1 Q
where L is given generally as an asymmetrical (3 s3) matrix. If, however, all components of the four
effects are known, then Eq. (5.18) could be used to check the internal consistency of the tensor prop
erties involved. This internal consistency check can be used on other interrelated rstorder effects.
P (5.20)
V
U
V
DEPENDENT COUPLED EFFECTS 91
Here, P is the pressure, U is the internal energy, and V is the volume, which is held constant. This
equation may be written in a more general form, applicable to crystal systems, if P is replaced by
Sij, dU is replaced by Vdu, and V is replaced by strain to give the Grneisen tensor as
ij
. (5.21)
ij u
But in the absence of any polarization and magnetization (P and M are zero under constant
E and B) and at constant strain, such that no mechanical work is done, we recognize that du = Tds
for any process in which reversible heat is absorbed by the system. Therefore, Eq. (5.21) becomes
1 ij , (5.22)
ij T s
ji
indicating that the Grneisen tensor is proportional to the inverse of the isometric piezocaloric
coefcient Aij1 (see Eqs. (4.55)), which is symmetrical.
Shown in Figure 5.5 is the interaction diagram that is descriptive of the Grneisen parameter
as presented in Eq. (5.22). Here, as before, the arrows point toward the dependent variable. From
the diagram, there results the tensor equation (note that the T s cancel)
1 ij
ij 1 /C cijkl kl (5.23)
T s
all taken at constant E, B, and E, and where CErepresents the heat capacity at constant strain, Akl is
the thermal expansion tensor, and cij represents the elastic stiffness moduli. The properties CE, Akl,
and cijkl can all be obtained in the region of zero strain, P and M, which satises the condition of
constant strain, and constant E and B.
T/C
T s
1
c
FIGURE 5.5: Interaction diagram descriptive of the Grneisen parameter.
92 TENSOR PROPERTIES OF SOLIDS
or in expanded form shown in Eq. (5.25). This holds generally for any of the seven crystal systems
with the proper choice of cij and Aj,.
1
c11 c12 c13 c14 c15 c16
1
c 22 c 23 c 24 c 25 c 26
2
2
3 c33 c34 c 35 c 36
3
C
1
4 c 44 c 45 c 46
4
Sym c 55 c 56
5
5
6 c66
6 (5.25)
Of particular interest is the Grneisen tensor specied for the cubic crystal system. See Sec
tion 6.2.5 and Table 6.3 for cubic elastic stiffness moduli. In expanded form, we can write
1
c 11 c12 c 12 0 0 0
1
c 11 c 12 0 0 0 1
2
1 c11 0 0 0 (c11 + 2c12) 1
3 = ,
0 C c 44 0 0 0 C 0
0 Sym. c44 0 0 0
0 c 44 0 0 (5.26)
giving the six components of G . From Eq. (5.26), it follows that the Grneisen invariant is
1 c 11 2c 12 K (5.27)
3 3C 3C s 11 2 s 12 C
which is the classical result, with K = (c11 + 2c12) / 3 being the bulk elastic modulus for the cubic
crystal system. The quantity K is also the reciprocal of the volume compressibility.
Because of its close relationship with stress (or strain), the Grneisen parameter may be de
composed into spherical and deviatoric components given by
ij ij i*j
(5.28)
where Gij* = Lij  G is the Grneisen deviator.
DEPENDENT COUPLED EFFECTS 93
There are other ways of representing the Grneisen parameter as can be seen from ve of the
six dependent coupled effects given by Eqs. (5.11)(5.13), (5.15), and (5.16). Keep in mind from
Figure 5.5 that the Grneisen tensor is the inverse of the piezocaloric coefcient, Aij1. However,
most of these other expressions involve axialmagnetic and/or rstrank property tensors that greatly
restrict their application in obtaining the components of Gij for many crystals. Eqs. (5.11) and (5.13)
would appear to be the most useful as alternative means of representing the Grneisen tensor.
95
CHAPTER 6
Before we can discuss the second and higherorder effects presented in the next chapter, it is neces
sary to lay a proper foundation for that discussion. The best means of accomplishing this is to revisit
the third and fourthrank tensor properties dened earlier in Section 4.5. We do this by consider
ing, as good examples, the piezoelectric and elastic effects.
The effect represented by Eq. (6.1) is called the direct piezoelectric effect, and dijk are the piezoelectric
moduli. Thus, dijk is a thirdrank polar tensor property relating a vector to a secondrank tensor,
hence, a vectortensor property.
If only pure stresses (no body torques) are applied, then Sjk Skj , which allows dijk dikj dim
and permits us to write the direct piezoelectric effect in the contracted form
However, because stress is a symmetric secondrank tensor Sjk Sjk , we follow the tensortomatrix
conversion rule (recommended in Standards on Piezoelectric Crystals, see Endnotes)
to avoid the appearance of factors of 2 in Eq. (6.2) in terms for which m = 4, 5, and 6. As a result,
we represent Eq. (6.2) as P = d:S or in matrix notation as
P dS. (6.5)
Recall that the double dot (:) indicates a double contraction product as in Eq. (2.47). In
expanded form, the three components of P in Eq. (6.5) can be written in the conformable matrix
array form given by
1
P1 d 11 d12 d13 d14 d15 d16 2
P d d 22 d 23 d 24 d 25
d 26 3
2 21
P3 d 31 d32 d 33 d 34 d 35 d 36 4
5
6 . (6.6)
Here, S1, S2, and S3 are the tensile stresses (positive by convention), and S4, S5, and S6 are shear
stresses, with the understanding that S23 S32 S4, S31 S13 S5, and S12 S21S6. Shown in Table
6.1 are ve common stress arrays. Note that for hydrostatic pressure p
S applied on each of the
axis normals.
The transformation law for piezoelectric moduli, d, can now be established. First, let P dS
be true relative to the old axes and let P a d aSahold relative to a new set of axes. Then, because
P and S transform as P a aP and Sa AS or S A
Sa, respectively, it follows that
THIRD AND FOURTHRANK TENSOR PROPERTIES 97
TABLE 6.1: Sample stress arrays assuming a symmetric stress tensor SijSji
1 0 0 1 0 0 0 0 0 0 0
0 0 2 0 0 0 = 0
Sym. 0 Sym. 0 Sym. Sym. 0 Sym. 0
da adA 1, (6.7)
where A is the quadratic transformation form as presented in Eq. (2.22). Equation (6.7) is the ap
propriate transformation law for the piezoelectric moduli and is identical to Eq. (2.31), assuming
^
that stress is a symmetrical secondrank eld tensor, S S
~
E dE (6.9)
in conformable matrix form. The single dot () indicates a single contraction product as in
Eq. (2.46). The converse piezoelectric effect is also called the rstorder electrostrictive effect, and dijk
are the rstorder electrostrictive moduli. From Eqs. (4.61) and (4.62), it is clear that the direct and
converse piezoelectric moduli are numerically equal.
98 TENSOR PROPERTIES OF SOLIDS
Because strain is usually a symmetrical secondrank tensor, Ejk Ejk, the tensor symmetry for
dijk becomes dijk dikj dim, which permits Eq. (6.8) to be written as
1 d11 d 21 d 31
d d 22 d 32
2 12 E
3 d 13 d 23 d 33 1 ~
E d E.
4 d 14 d 24 d 34 2
E 3
d d 25 d 35
5 15
6 d 16 d 26 d 36 (6.11)
Equation (6.11) is valid because the symmetric part of the strain tensor Ejk, dened by Eq.
(2.17), is
1
jk 2 ( jk kj ) , (6.12)
1 1
11 12 31 1 2
6 2
5
22 23 2 1
4 ,
2
Sym. 33 Sym. 3 (6.14)
where E1, Eand E are the elastic tensile strains or stretches, and the three remaining, E4, Eand
E, are the elastic shear strains. As a result of the conversion scheme of Eq. (6.14), the shear strain
components of Eq. (6.10) will have factors of on both sides of the equations that cancel. This
THIRD AND FOURTHRANK TENSOR PROPERTIES 99
permits Eq. (6.11) to be written in simple twosubscript form exclusive of the factors of 2 in the
shear components that would otherwise be present. As it turns out, matrix shear strain is identi
cal to engineering shear strain (i.e., E Gyz, E Gzx, and E Gxy ). The antisymmetrical part of Ejk is
the axial secondrank tensor given by Vjk
Ejk
Ekj which is the rotation resulting from elastic
shear.
The transformation law for converse piezoelectric moduli, d, is now established in a manner
^
similar to that for the direct effect given earlier. First, let Ed E be true relative to the old axes and
^
let Ead aE a hold relative to a new set of axes. Now, because E and E transform as EaA^
1E and
E aaE or E a^E a (a
1 a^), respectively, it follows that EaA ^
1d^EA^
1 d^a^E ad^aE afrom
^
1EA
which we conclude that
~ ~1 ~ ~
d da. (6.15)
The transformation for matrix shear strain, Ea A^
1E, results from the tensortomatrix conver
sion rule given by Eq. (6.14). Note that A^
1 requires two separate operations because A^ x A
1
in general.
For example, all holohedral crystal systems, those represented as Xin Table 3.6, are centrosym
metrical, and as a result, dijk
dijk 0. Thus, the 11 centrosymmetrical crystal groups will be lacking
in all piezoelectric moduli.
To illustrate, we apply Neumanns principle to the 222 crystal group. By using Table 3.6, we
observe that the 222 group requires the use of generating matrices s(2) and s(3). From Table 3.5, the
transform of axes are given in compact form according to
1 1 1 1
(2) (3)
s 2 2 and s 2 2
3 3 3 3 (6.17)
100 TENSOR PROPERTIES OF SOLIDS
and are applied in any sequence. Applying s(2) rst, it is clear that dijk 0 for all moduli containing an
odd number of 1s and/or 3s. Application of s (3) requires that dijk 0 for all moduli for which there is
an odd number of 1s and/or 2s. Therefore, the only moduli to survive are those containing all three,
1, 2, and 3 in any order. As a result, the array of piezoelectric moduli becomes
in both three and twosufx notation. Application of Neumanns principle to the trigonal or hex
agonal crystal systems requires the bruteforce method involving Eq. (6.7) for all threefold and
sixfold rotations.
As an example, let us apply Neumanns principle to the hexagonal class 6. From Table 3.6,
we see that this requires the application of generating matrices s(3) s(7) = s(14). To simplify the cal
culations, it is advantageous to apply s(3) rst, then follow with s(7) as required by the bruteforce
method. From generating matrices given by Eq. (6.17), application of s(3) allows the dijk to survive
only for moduli with an odd number of 3s, a total number of eight independent moduli. When
this is done, application of s(7) to the piezoelectric transformation law given by Eq. (6.7) takes
the form
THIRD AND FOURTHRANK TENSOR PROPERTIES 101
(3)
s(7) [dijk] s (
) 1
41 3
4 0 0 0 2
3
43 1
0 0 0 23
12 2
3
0 0 0 0 d 123 d 131 0 0
4
0 1 0 0 0 .
d 3 1 0 0 0 d 223 d 231 0 0
2 2 0 3
0 0 12 0
d 311 d 322 d 333 0 0 d 312 2
0 0 1
0 3
0 0 2 12 0
43 4
3
0 0 0 12
(6.19)
When the matrix multiplication operations of Eq. (6.19) are carried out, there result the following
equations relating the old moduli to the new moduli:
d 123 3 1 d 3 d311 3 3
d123 d223 131 d231 3 d311 = + d322 d
4 4 2 2 2 4 4 4 312
1 d123 3 d131 3 3 d 3
d131 d223 3 d d322 = d311 + 322 + d
2 2 2 4 4 231 4 4 4 312
3 d 1 3 d
d223 = d123 + 223 d131 231 3
4 4 2 2 2 d333 = d333
1 3 d 3 d
d231 = d123 223 3+ d131 231 3 3 d
d312 = d311 d322 312
2 2 2 4 4 2 2 2
Solving these eight equations simultaneously gives the following class 6 piezoelectric moduli in
both three and twosufx notation where the eight independent moduli in Eq. (6.19) have been
reduced to four in Eq. (6.20).
0 0 0 d123 d131 0 0 0 0 d 14 d 15 0
0 0 0 d 131 d 123 0 0 0 0 d 15 d 14 0
d 311 d 311 d 333 0 0 0 d31 d31 d33 0 0 0 (6.20)
From Table 3.6, we note that the generating matrices for class 622 are s(12) and s(14). Because
the moduli arrays of Eq. (6.20) result from the application of s(14), there remains only the applica
tion of s(12) s(1) s(4) to the threesufx form of Eq. (6.20) to obtain the moduli for class 622. From
Table 3.5 for s(12) and using the method of direct inspection, it is clear that the only moduli to survive
102 TENSOR PROPERTIES OF SOLIDS
are those for which an odd number of 1s exists. Thus, d131 d311 d333 0, resulting in the array for
class 622 given by
0 0 0 d123 0 0 0 0 0 d14 0 0
0 0 0 0 d123 0 0 0 0 0 d14 0 .
0 0 0 0 0 0 0 0 0 0 0 0 (6.21)
Continuing on to class 6mm, we see from Table 3.6 that the generation matrices required for
this crystal class are s(3), s(4), and s(7). So there remains only the application of s(4) in Table 3.5 to the
threesufx result of matrix arrays (6.20). When this is done, the only moduli to survive are those
for which an even number of 1s or no 1s exist. Thus, d123 0 in arrays (6.19) resulting in the moduli
arrays for class 6mm given by
0 0 0 0 d131 0 0 0 0 0 d15 0
0 0 0 d131 0 0 = 0 0 0 d15 0 0
d 311 d 311 d 333 0 0 0 d 31 d 31 d 33 0 0 0 (6.22)
By applying similar analyses to the 32 crystal classes, there result the matrices for the direct
and converse piezoelectric moduli given in Table 6.2 where dijk 0 for all centrosymmetrical classes.
TABLE 6.2: Piezoelectric moduli for both the direct and converse effects
Triclinic
Class 1
d 11 d 12 d 13 d 14 d 15 d 16
d 21 d 22 d 23 d 24 d 25 d 26
d 31 d 32 d 33 d 34 d 35 d 36

Class centrosymmetrical, dijk 0
Monoclinic
Class 2 (2 x2) Class m (m >x2)
0 0 0 d 14 0 d 16 d 11 d 12 d 13 0 d 15 0
d21 d 22 d23 0 d 25 0 0 0 0 d24 0 d 26
0 0 0 d34 0 d 36 d 31 d 32 d 33 0 d 35 0
Orthorhombic
0 0 0 0 d 15 0 0 0 0 d 14 0 0
0 0 0 d 24 0 0 0 0 0 0 d25 0
d 31 d 32 d 33 0 0 0 0 0 0 0 0 d36
Tetragonal
_
Class 4 Class 4
0 0 0 d14 d 15 0 0 0 0 d 14 d 15 0
0 0 0 d 15 d 14 0 0 0 0 d 15 d 14 0
d 31 d 31 d 33 0 0 0 d 31 d 31 0 0 0 d 36
0 0 0 0 d15 0 0 0 0 d 14 0 0
0 0 0 d 15 0 0 0 0 0 0 d 14 0
d31 d 31 d 33 0 0 0 0 0 0 0 0 d 36
Class 422
0 0 0 d 14 0 0
0 0 0 0 d 14 0
0 0 0 0 0 0
Trigonal
3m
Class 3 Class (m >x1)
d 11 d 11 0 d 14 d 15 _ 2d 0 0 0 0 d15 2d 22
22
_ d 14 2d 11 d22 d 22 0 d 15 0 0
d 22 d 22 0 d 15
d 31 d 31 d 33 0 0 0 d31 d31 d 33 0 0 0
Class centrosymmetrical, dijk 0
Class 32 (quartz)
d 11 d 11 0 d 14 0 0
0 0 0 0 d 14 2d 11
0 0 0 0 0 0
Class m centrosymmetrical, dijk 0
Hexagonal
_
Class 6 Class 6
0 0 0 d 14 d 15 0 d 11 d 0 0 0 2d 22
11
0 0 0 d 15 d 14 0
0 0 0 2 d 11
d 22 d 22
d 31 d 31 d 33 0 0 0 0 0 0 0 0 0
Class centrosymmetrical, dijk 0
Class 6mm (same as 4mm ) Class 622 (same as 422)
0 0 0 0 d 15 0 0 0 0 d 14 0 0
0 0 0 d 15 0 0 0 0 0 0 d 14 0
d31 d 31 d 33 0 0 0 0 0 0 0 0 0
_
Class 62m
d 11 d 11 0 0 0 0
0 0 0 0 0 2 d 11
0 0 0 0 0 0
Class mmm centrosymmetrical, dijk 0
THIRD AND FOURTHRANK TENSOR PROPERTIES 105
Cubic
_
Class 23 and 4 3m Class 432
0 0 0 d 14 0 0 0 0 0 0 0 0
0 0 0 0 d 14 0 0 0 0 0 0 0
0 0 0 0 0 d 14 0 0 0 0 0 0
To demonstrate the use of the piezoelectric moduli in Table 6.2, we will work a couple of
problems involving quartz, which belongs to the crystal class 32. Consider the direct piezoelec
tric effect represented by Eq. (6.2) as applied to class 32 and the application of normal and shear
stresses. Shown in Figure 6.1(a) is the array of piezoelectric moduli for class 32 together with the
corresponding polarization and stress components. In Figure 6.1(b) is the stereogram for class 32
giving the x1 and x2 axes in the (0001) plane with its normal along the threefold (optic) axis, x3.
Clearly, there are only two independent piezoelastic moduli, d11 and d14.
Referring to Figure 6.1 for quartz, a polarization P1 can be produced along the x1 direction
under the following conditions:
1. By a tensile stress S applied along the x1, resulting in P1 d11S1, where P2 P3 0.
2. By a compressive stress S applied along x1, resulting in P1
d11S2 where P2 P3 0.
3. By a shear stress S4 S23, resulting in P1 d14S4, where P2 P3 0.
Normal Shear
y'
{
{
1 2 3 4 5 6 z,x3
P1 d11 d11 0 d14 0 0 Along x1 y
P3 0 0 0 0 0 0 Along x3 x,x1
(a) (b)
FIGURE 6.1: (a) Piezoelectric moduli for quartz (class 32) and the corresponding polarization and
stress components. (b) Stereogram for class 32.
106 TENSOR PROPERTIES OF SOLIDS
A polarization P2 along x2 can be produced only by negative shear stresses S31 and S12 giving
P2
d14S31 and P2
d11S12, where for both P1 P3 0. From Figure 6.1(a), it is evident that a
polarization P3 along x3 is not possible under any set of conditions.
1.
11 d 11
P1 d 111 (6.23)
Here, d1a, measures the longitudinal piezoelectric effect in the x1x2 plane, meaning the charge per
unit area on the surface of a plate divided by the force per unit area applied normal to that surface,
which is in the 0x3 direction. To nd d1a, we will need to nd A
by making use of the equations
Sa^Saa A
Sa, which are the inverse of Eqs. (2.21) and (2.22). Recall that the stress tensor is a
symmetric secondrank tensor. Once A
is known, then d1a, can be found from the transformation
equation d aadA
, where a given moduli array is chosen from Table 6.2. As an example, we will
nd d1a for a quartz crystal. Shown in Figure 6.2 is the longitudinal direction 0x a1 and direction co
sines relative to a set of coordinate axes such that lie in the (0001) plane of a quartz crystal. Thus, as
required, the surface of the crystal must conform to the point group symmetry.
Because a polarization cannot be produced alone 0x3, a direction 0xa1 out of the x1x2 plane will
produce a polarization only due to the projection of 0xa1 onto the x1x2 plane. Thus, we are entitled,
but not required, to set a13 l3 0, not shown in Figure 6.2. To facilitate the calculations, we will
make the following transformation simplications: a11 l1, a12 l2, a13 l3, with mi and ni used for
the remaining direction cosines following Eq. (3.24). First, we will nd A
as follows:
l1 m1 n1
1 0 0
l1 l2 l3
l 12 l1 l2 l3 l1
a% a l2 m2 n2 0 0 0 m1 m2 m3 l1 l2 l22 l2 l3 1 .
l
3
m3 n3 0 0 0 n1 n2 n l l
3 3 1
l2 l3 l 2
3 (6.24)
1 l12 0 0 0 0 0 1
2
2
l2 0 0 0 0 0
0
l2 0 0 0 0 0
0
1
3
3
.
4
l2 l3 0 0 0 0 0
0
l l 0 0 0 0 0
0
5
3 1
6
l1 l2 0 0 0 0 0
0
(6.25)
THIRD AND FOURTHRANK TENSOR PROPERTIES 107
x2
x'2 x'1
cos12
90 o 
cos11
x3 x1
0
FIGURE 6.2: Longitudinal direction x1 relative to a set of coordinate axes, where x1 and x2 lie in the
(0001) plane of crystal class 32.
Now with A
known, we will set up the matrix equation for d aadA1 where d is the class 32 array
obtained from Table 6.2. Thus, there results
l1 l2 l 3
d 11 d 11 0 d 14 0 0
d m1 m2 m3 0 0 0 0 d14 2d 11 1 a d 1
n 1 n 2 n 3 0 0 0 0 0 0
l 12 0 0 0 0 0
l 22 0 0 0 0 0
l1 d11 l1d11 0 l1d14 l2 d14 2l 2 d11 .
l 32 0 0 0 0 0
m1d11 m1d11 0 m1d14 m2 d14 2m2 d 11
l 2 l3 0 0 0 0 0
n1d 11 n1d 11 0 n1d 14 n2d 14 2n2 d 11
l3 l1 0 0 0 0 0
l1l 2 0 0 0 0 0 (6.26)
Therefore,
d11 l13 d11 l1 l22 d11 l1 l2 l3 d14 l1 l2 l3 d14 2 l1 l22 d11
l13 d11 3 l1 l22 d11 l1 ( l12 3 l22 ) d11 , (6.27)
which is seen to depend only on d11. Furthermore, from Figure 6.2, it follows that l1 cosQ and
l2 cos(90o
Q sinQ. Therefore, with the help of trigonometric identities, we nd
d11 d11 cos (cos2 3 sin2 )
d11 cos (cos2 3 cos2 3)
d11 ( 4 cos3 3 cos ) d11 cos 3 . (6.28)
The result d1ad11 cos 3Qforms a threepetal (each almond shaped) rosette in the (0001) plane, in
dicating that the polarization is a maximum along the directions x, y, and y a spaced 120o apart (see
Figure 6.1(b)) and that it is zero at 60o intervals between the x, y , and y a directions.
108 TENSOR PROPERTIES OF SOLIDS
1 0 0 0 0 0 2l 1m 1 0
0 0 0 0 0 2l2m 2
0
2
0 0 0 0 0 2l3m 3
0
3
1
4
0 0 0 0 0 l2m 3 l3m 2
0
5
0 0 0 0 0 l3m 1 l1m 3
0
(6.29)
6
0 0 0 0 0 l1m 2 l2m 1
6
Knowing A
1 permits us to evaluate d aad A
1, which will be more complex to evaluate than in the
case of the longitudinal effect given by Eqs. (6.26), (6.27), and (6.28).
6.2 ELASTICITY
The concept of elasticity can best be understood by considering a onedimensional lattice shown
in Figure 6.3. Here, the equilibrium condition is demonstrated in Figure 6.3(a), where the lattice
parameter is given by a0. Then, if a tensile force is applied along the 0x direction the atoms are
displaced by an amount l a
a0 to an atom separation of a as in Figure 6.3(b). At a state of equi
a0 a
f f
(a) (b)
FIGURE 6.3: A onedimensional lattice. (a) Atoms at equilibrium with lattice parameter a0. (b) Atoms
reversibly displaced after the application of a tensile force f along the 0x direction.
THIRD AND FOURTHRANK TENSOR PROPERTIES 109
+ a0
Binding
Energy 0 l
E(l)
_
Force
f(l) 0 l
Repulsion
f=0
FIGURE 6.4: Binding energy and tensile force showing position of stability in a onedimensional lattice.
librium, the force f0 would represent a shortranged attractive force between atoms along 0x where
the lattice parameter between atoms is maintained at a0.
The binding energy of the atoms in the onedimensional lattice is a function of the atom
displacement l and is shown in Figure 6.4. Here, at static equilibrium, the minimum in the energy
curve occurs at
(dE / dl )l 0 0, (6.30)
for which the applied tensile force f 0 and where a a0. So, as f m 0, a position of stability between
the atoms is approached. Of course, the force f can be either a tensile force r a compressive force.
The convention followed in this text is as follows:
In any case, the cohesive force between atoms is a reversible function of displacement.
110 TENSOR PROPERTIES OF SOLIDS
dE 1 d2E 2 .. .
E ( l ) E0 l l .
d l (0) 2 d l 2 (0) (6.31)
For very small l, small linear strains exist, and applying Eq. (6.30), we have
1 d2 E
E ( l ) E0 l 2 ....
2 d l 2 (0) (6.32)
Taking the derivative of Eq. (6.32) with respect to displacement l leads to Hookes law given as
d E(l ) d2 E
f l Yl,
2
dl d l (0) (6.33)
where
d2 E
Y Young's Modulus.
2
d l (0) (6.34)
Here, Youngs modulus (d2 E / dl 2) is the curvature of the E(l ) versus l curve in Figure 6.4. Thus,
the sharper the minimum in the E(l ) versus l curve, the greater will be the Youngs modulus, Y, and
vice versa.
f stress
l strain. (6.35)
Now, the two alternative forms of Hookes law may be expressed in terms of the new parameters,
S and E, as
THIRD AND FOURTHRANK TENSOR PROPERTIES 111
c , (6.36)
s
where
Following the developments given in Section 6.1 with regard to stress and strain, we can
express Hookes law ScE in tensor and matrix form, respectively, as
and
Here, the rst and last sufx pairs of cijkl permit the cmn coefcients to be unfolded according to the
following scheme.
where, as before in Section 6.1, S1, S2, and S3 are the tensile stresses (positive by convention) and S4,
S5, and S6 are shear stresses, with the understanding that S23 S32 S4, S31 S13 S5, and S12 S21
S6. With the convention used in Eq. (6.14), the strains E,Eand E are the elastic tensile strains or
stretches, and the three remaining, E,Eand E, are the elastic shear strains.
112 TENSOR PROPERTIES OF SOLIDS
which represents nine equations each with nine termsa total of 81 sijkl coefcients. Equation (6.42)
can be represented in the simplied matrix form
provided that 2s and 4s are introduced into the denitions of simn according to the following:
These denitions avoid the appearance of the 2s and 4s in Eq. (6.42), thereby making the simpli
ed matrix form possible. Note that in the case of Eq. (6.38), no introductions of 2s and 4s were
necessary to allow Eq. (6.41).
By the thermodynamic arguments presented in Section 4.4, we can write
SaAS. Then referring to the developments leading to Eq. (6.15), the strain transforms to the new
^
E or EA
axes as EaA ^Ea. Therefore, it follows that SaASAcEAcA
^Eac aEa, or nally,
~.
c c (6.46)
A procedure similar to that for the stiffness coefcients is followed for the elastic compliance
coefcients. Let EsS and Eas aSa be valid for the old and new axes, respectively. From the pre
^
EA^
sSA^
sA
SasaSafrom which results
ceding, SA
Sa such that we can write EaA
~ 1 s 1
s = , (6.47)
^. Here, A^
is the transpose of the inverse of A, two operations.
where it is understood that A
xA
or
for a reversible, isothermal deformation in the absence of all electrical and magnetic elds and their
conjugate effects. For a linear elastic solid under these conditions, Si dEi Ei dSi.
Making use of the substitution property of the Kronecker delta Dij (see Section 2.6.3), there
results Ej Dij Ei permitting Eq. (6.48) to be integrated for the elastic strain energy density
wElastic ci j
( ij i ) di 1
2
cij ( ij i2 ) C
1 cij i j 1
i i
2 2
(i 1
6), (6.50)
where the constant of integration C0 because welastic0 if EiEj0. For the total strain energy,
Eq. (6.50) must be integrated over the volume of the deformed crystal,
ETotal V i i dV . (6.51)
polar tensors of even rank are centrosymmetrical. This means that by Neumanns principle, their
property coefcients are left unchanged by the transformation operation of a center of symmetry.
The procedure to be followed for property coefcients of polar fourthrank tensor properties
is as follows:
1. Use the method of direct inspection for all crystal classes for which the s generating
matrices, other than s , are required as indicated in Table 3.6. This method provides the
easiest means of obtaining the independent coefcients of polar fourthrank tensors. The
10 possible generating matrices are given in Table 3.5 for both s and quadratic S forms. In
applying the direct inspection method to the two sufx coefcient arrays in Eqs. (6.41) and
(6.45), the four sufx notation they represent must be kept in mind. Remember that it is
actually the four sufx notation to which the method of direct inspection is applied via the
tensor/matrix notation of Eq. (6.39).
2. The bruteforce method must be used in applying the generating matrix S to the tri
gonal and hexagonal crystal systems of polar fourthrank tensor properties. However,
if generating matrices other than s are involved in the particular crystal class, apply
them rst each in turn by using the method of direct inspection to obtain a simpli
ed array of the moduli. By using the appropriate transformation law, c a A c A ^ or
^
sA
, complete the matrix calculations with the generating matrix S , together
s a A
with its inverse and transpose as needed, to obtain a set of equations for the new property
moduli. As a nal step, equate each of the old moduli with the new and solve the resulting
set of equations simultaneously for the moduli appropriate for the given crystal class. It is
strongly recommended that application of the bruteforce method be computer assisted.
As an example, let us apply the method of direct inspection to the centrosymmetrical cubic
crystal class \\m3\\having the generating (s) matrices s(4) and s(10) given in Table 3.6 and their respec
tive generation operators provided in Table 3.5. Referring to the tensor/matrix sufx notations of
Eq. (6.39), we apply the transformation of axes for the generating matrices s(4) and s(10) as follows:
1 0 0
s (4)
(m x) 0 1 0
0 0 1
This means that all c stiffness moduli in Eq. (6.41) containing a single 5 or single 6 (but not contain
ing both) are zero. As examples, c15 c1131 0, c25 c2231 0, c46 c2312 0, and so forth, for a total of
eight vanishing coefcients. Application of s(10) then follows accordingly:
THIRD AND FOURTHRANK TENSOR PROPERTIES 115
0 1 0
s (10)
( 3[111] ) 0 0 1
1 0 0
Together with s(4), this means that c16 c24 c2223 0, c36 c14 c1123 0, and so forth. Also, c11 c22
c33, c44 c55 c66 , and c12 c23 c31.
If, for class \\m3m\\, the transformation of axes for s(4) and s(9) together with that for s(10) is
applied to the remainder of the cubic classes, the results are found to be the same as above. Thus,
the elastic stiffness and compliance coefcients for all classes of the cubic system are given by the
following arrays in which there are three independent coefcients, c11c12 c44, and s11 s22 s44:
Continuing in this way, the independent elastic stiffness coefcients are identied for the remainder
of the seven crystal systems and are presented in Table 6.3. The case of an isotropic solid is added for
completeness and will be considered separately below as an extension of the cubic crystal system.
TABLE 6.3: The independent elastic stiffness coefcients for the seven crystal systems with the
addition of the case for the isotropic solid
Triclinic
c 11 c 12 c 13 c 14 c 15 c 16
c 22 c 23 c24 c 25 c 26
c33 c 34 c 35 c 36
c44 c 45 c46
Sym. c55 c 56
c66
116 TENSOR PROPERTIES OF SOLIDS
Monoclinic
Orthorhombic
Tetragonal
_ _
4, 4, 4 / m 4mm, 42m, 422, 4 / mmm
c 11 c 12 c 13 0 0 c 16 c 11 c 12 c13 0 0 0
c 11 c 13 0 0 c 16 c 11 c 13 0 0 0
c 33 0 0 0 c 33 0 0 0
c 44 0 0 c 44 0 0
Sym. c 44 0 Sym. c 44 0
c 66 c 66
THIRD AND FOURTHRANK TENSOR PROPERTIES 117
Trigonal
_ _
3, 3 3m, 32, 3m
c 11 c 12 c 13 c 14 c 25 0 c 11 c 12 c 13 c 14 0 0
c 11 c 13 c 14 c25 0 c 11 c 13 c14 0 0
c 33 0 0 0 c 33 0 0 0
c44 0 (c 25 ) c 44 0 0
Sym. c 44 (c14 ) Sym. c 44 (c14 )
{ 1
2 }
( c 11 c12 )
{ 1
2 }
(c 11 c 12 )
1
2
( c11 c 12) 2 (s11 s12 )
Hexagonal
_ _
6, 6, 6 / m 6mm, 622, 62m, 6 / mmm
c 11 c 12 c 13 0 0 0
c 11 c 13 0 0 0
c 33 0 0 0
c 44 0 0
Sym. c 44 0
{ 1
2
( c11 c12)
}
Cubic
_
23, m3 432, 432, m3m
c 11 c 12 c 12 0 0 0
c11 c 12 0 0 0
c 11 0 0 0
c 44 0 0
Sym. c 44 0
c 44
118 TENSOR PROPERTIES OF SOLIDS
Isotropic
c 11 c 12 c 12 0 0 0
c 11 c 12 0 0 0
c 11 0 0 0
{ 1
2
( c11 c12) } 0 0
Sym. { 1
2
(c 11 c12) } 0
{ 1
2 }
(c 11 c 12 )
1
2
(c 11 c 12 ) 2( s11 s12 )
The classes to which a given coefcient array belongs are indicated above the array. Note that the elastic compliance coefcients sij
are obtained from the elastic stufness coefcients by replacing c by s except where noted by parentheses and braces {x}.
x3, z
450
x2'
x2, y
x1'
x1, x
(6.52)
Introducing the results of Eq. (6.52) into Eq. (6.43) for the cubic system yields
11 12
s11 0 0 0
0
0
Sym. s44 0
0
0
s44
0
0
(6.53)
Therefore, by Eq. (6.53), we have Ea12 [(s11
s12) / 2 (s11
s12) / 2] Sa12 (s11
s12) Sa12 where use
of the matrixtotensor strain conversion of Eq. (6.14) yields the results
E6a 2E12
a 2(s11
s12)S6a s44S6a or s44 2(s11
s12) (6.54)
as the necessary and sufcient condition for elastic isotropy, in agreement with Table 6.3. Obviously,
the application of any other pure shear stress, SaorSa, would lead to the same result.
Let us now compare the elastically isotropic compliance array in Table 6.3 with those fre
quently found in engineering textbooks:
1 1 / Y /Y /Y 0 0 0 1
1 /Y /Y 0 0
0
2
2
3
1 /Y 0 0 0
3
4
1/G 0 0
4
Sym. 1/G 0
5
5
6
1 / G
6
(6.56)
where Y is Youngs modulus, N is Poissons ratio, and G is thes modulus of rigidity with the combined
relation, derived from Eq. (6.57), given by
Here, Y is a measure of the elongation of an elastically isotropic solid under tension, and N is a mea
sure of the transverse contraction (at right angles to the elongation). The rigidity modulus measures
the stufness to shear.
1' x3
x1'
x3' x2
x2' x1
(a) (b)
FIGURE 6.6: (a) Application of a unit tensile stress to a crystal rod along the 0x1a direction. (b) Orienta
tion of the rod axis 0xa1 relative to reference axes 0xi.
THIRD AND FOURTHRANK TENSOR PROPERTIES 121
From Eq. (6.57), Youngs modulus can be dened in the 0x1a direction as
where it is understood that Sa is a unit tensile stress applied along the 0x1a axis of the rod such that
SaSaSaSaSaReferring to Figure 2.1, let the direction cosines for 0x1a in Figure 6.6(b)
relative to reference axes 0xi be represented as follows: a11 l1, a12 l2, and a13l3. Then, sa11 is found
for any crystal system by Eq. (6.47), which is
~ 1 s 1
s (6.60)
or
But (l 41 l 42 l 43 ) (l 21 l 22 l 23 )
2(l 22 l 23 l 23 l 21 l 21 l 22) which, when introduced into the equation for
sa11, yields the wellknown result
s11
1
Y
s11 { s44 2 ( s11 s12 )} (l 2 2
l l32 l12
2 3
)
l12 l22 , (6.61)
which is not isotropic. Now, as examples, let 0x1a ;uvw=, such that
l1 = u / u 2 + v 2 + w 2 , l2 = v / u 2 + v 2 + w 2 , l3 = w / u 2 + v 2 + w 2
1
Y<uvw> 1
= Y<100> + 3 (Y<111>
1 1
Y<100> ). (6.62)
The results for other crystal systems can be found in Nye cited in Endnotes.
The method of solution is the same as for Youngs modulus, namely, saA^
1 sA
1, where A
1 is found
from Sa^Saa and SA
1Sa. After simplifying the result, the rigidity modulus is
which is easily seen not to be isotropic. If we take [uvw] 0x1a and [hkl ] 0xa2, then
Poissons ratio, dened as v
EaEa
EaEa, is more difcult to obtain by using the pro
cedure above. However, knowing Y and G, it is easily found from Eq. (6.58) to be
Y / 2 G 1. (6.65)
123
CHAPTER 7
First, as we move into a discussion of the second and higherorder effects, it quickly becomes ap
parent that their number is far too large for a detailed inclusion in this text. However, we will give
specic examples, for instructional purposes, and then provide a generalized approach to their de
velopment. Second, it is often the case that the secondorder effects do not depend strongly on the
magnitudes of the intensive and extensive parameters and may be regarded as weak correction terms
(if they exist at all) to the rstorder effects under a given set of small intensive or extensive elds.
Remember that the rstorder effects were developed under the assumption of innitesimally small
elds. However, some secondorder effects may actually dominate the rstorder effects particularly
under eld strengths that are not innitesimally small. If the secondorder effects are but weak cor
rection terms to the rstorder effects, then it is safe to say that the third and higherorder effects
may be disregarded as we do in our treatment.
which applies for very small electric elds and very small stresses and strains all at constant T, B,
and S. At large stresses and strains, quadratic (secondorder) terms must be introduced. To do this,
we can expand dijk in a Taylor series to give
d 1 2dijk
dijk = dijk0 + ijk El + E E + , (7.2)
El T , B, 2 El Em T , B, l m
where dijk0 is the value for dijk at innitesimal eld strength. Introducing Eq. (7.2) into Eq. (7.1) gives
the result
124 TENSOR PROPERTIES OF SOLIDS
0
ij dijk
ijkl
El Ek , (7.3)
where the thirdrank tensor terms Gijkl El are the correction terms to dijk0 proportional to eld
strength and that must conform to both tensor and crystal symmetry.
All electrostrictive moduli dijk0 vanish for the 11 centrosymmetrical crystal classes given in
Table 3.4. However, the correction terms Gijkl El are not centrosymmetrical and can create new
electrostrictive moduli proportional to the eld strength E and a strain proportional to E 2. These
new moduli create what is called a morphic effect. Thus, an electrostrictive effect in a centrosym
metrical class can exist but only as a morphic effect.
,
ijkl jikl ijlk jilk mn (7.5)
Solving for Ea by acknowledging the transformation for the dyadic EE and using Eq. (7.6), there
results
^
E and
EaA (EE)aA(EE) or (EE)A
(EE)a
^
EA
Therefore, EaA ^
G(EE)A
^
GA
(EE)aG(EE)a, resulting in the transformation form
SECOND AND HIGHERORDER EFFECTSSYMMETRY CONSIDERATIONS 125
~1 1,
(7.7)
which transforms exactly like the elastic compliance coefcient, s aA^
sA
given in Eq. (6.47).
a = a ( , , , )b ,c , ...
b = b ( , , , )a ,c , ...
(7.8)
Similarly, the state equations for the intensive parameters are
(a ,b, c , ), ,
( a , b, c , ), ,
(7.9)
We now expand each state equation in Eqs. (7.8) in a differential Taylors series with the result
1 n
da = d
+ d + d + a ( , , , )
n=1 n ! b, c,
1 n
db = d
+ d + d + b ( , , , )
n=1 n ! a, c,
M M (7.10)
Similarly, the Taylor series expansion of the intensive state equations in (7.9) become
1 n
d d a db dc (a , b , c ,)
n 1 n ! a b c
,
,
1 n
d d a db dc (a , b, c, )
n 1 n ! a b c
,
,
M M (7.11)
Now, for the sake of illustration, consider any two intensive parameters A and B and their
corresponding (conjugate) extensive parameters a and b with all other extensive parameters held
126 TENSOR PROPERTIES OF SOLIDS
constant, i.e., G,D, ... constant. Then, if Eqs. (7.10) apply to the compliance effects as in Eq. (4.26),
we can use Taylors expansions to evaluate the integrals da and db, giving
1 C 1 C
a, a,
a C a, C a, 2 2 (7.12)
2 2
1 C 1 C
b, b,
b C b,
C
b,
2
2 , (7.13)
2 2
where now $AA
A and $BB
B, indicating that the Taylor series (7.12) and (7.13) are to be
evaluated around initial values A0 and B0 that become vanishingly small. After differentiating Eqs.
(7.12) and (7.13), there results
(C a, ) (C a, )
d a = (C a, ) d + (C a, ) d + d + d + (7.14)
(C b, ) (C b, )
d b = (C b , ) d + (C b, ) d + d + d + , (7.15)
where use was made of
d
l im ( )2 2 d and d l im ( ) 2 2 d . (7.16)
0
0
0 0
If only the rst and secondorder effects are considered, Eqs. (7.14) and (7.15) can be rep
resented approximately in the matrix form
C a,
a, C a,
C a, C
d a d .
d b d
C b, C
b, C b,
b,
C
(7.17)
Here, other secondorder terms such as u2a / uAuB and u2b / uAuB together with the third and
higherorder terms have been neglected. We will revisit the issue of rst and secondorder terms
later when we consider the phenomenological development of the optical effects.
Assuming that Eqs. (7.17) are a valid approximate representation of the extensive differen
tials da and db as functions of the intensive A and B, then an interesting and useful relationship
between the secondorder terms can be derived. Since from the application of Stokes theorem in
Eq. (4.38), we established the symmetrical nature of the compliance effects given by Cmn Cnm , it
SECOND AND HIGHERORDER EFFECTSSYMMETRY CONSIDERATIONS 127
follows that a symmetrical relationship can also be established between the secondorder effects in
Eqs. (7.17). Thus,
C a,
a b
C b,
(7.18)
permits
C a, b C b,
(7.19)
and
C b, C a,
a
(7.20)
because the order of differentiation is immaterial. The meaning of (u(Cb,B)A/uA)B in Eq. (7.19) is that
Cb,B is evaluated at constant A and that its change with A is evaluated at constant B. The expressions
in Eqs. (7.19) and (7.20) are secondorder Maxwell relations. Introducing these expressions into
Eqs. (7.17) gives the results
a,
C b,
C a,
C a,
C
d a d
.
db
d
C b,
C a,
b, C b,
C
(7.21)
By thermodynamic symmetry, the Maxwell relations lead to the equality of cross (bracketed) terms
C b,
C a,
C a,
C
,
b,
(7.22)
where it follows that
C b, C a,
.
(7.23)
Note that the expressions in Eq. (7.23) result from the symmetry expressed by Eq. (7.18) and that
the secondorder cross terms in Eqs. (7.21), (7.22), and (7.23) are no longer multiplied by an inten
sive parameter that is not held constant as in the case of Eqs. (7.17).
128 TENSOR PROPERTIES OF SOLIDS
Consider the use of Eqs. (7.21) to develop the rst and secondorder electrostrictive effects
as was done in Section 7.1, but from a different approach. To do this, we select the following exten
sive and intensive parameters:
a = =
= .
b P = E (7.24)
Equations (7.21) now become
, C P,E
C , C
,E
C E
E
E E E
d d
,
d P d E
C ,
P, E C
P, E
C P , E E
C E
E E T ,B (7.25)
where it is understood that T and B are held constant. By thermodynamics symmetry, the cross
(braced) terms are equal giving the results
C P, E
C ,
E
E E ,
C ,E
E C P,
(7.26)
E
C P , E
C ,
E ,
E (7.27)
E E
because (C E,E)S (CP,S)E . The compliances CP,E and C E,S are dened by Eqs. (4.45) and (4.47), re
spectively. Written in tensor notation, Eq. (7.27) becomes
j
s
0 i E l ijkl lm ijk . (7.28)
kl E
Em
What Eq. (7.28) indicates is that the components of the polar thirdrank tensor Yijk on left side of
the equation are numerical equal to those on the right side or vice versa. However, the frequency of
the E and S eld changes must be the same if the equality of Eq. (7.28) is to be valid.
As another approach to the evaluation of secondorder effects, consider the application of the
parameter selection in Eq. (7.24) to Eqs. (7.17) expressed as
SECOND AND HIGHERORDER EFFECTSSYMMETRY CONSIDERATIONS 129
, C , ,E C ,E
C E C E
E
E
d d .
d P dE
C P , P , E C
P , E
C P , C E
E
E
E (7.29)
The rst and secondorder converse piezoelectric (electrostrictive) effects are represented by
the equation for dE under constant stress S given in tensor notation by
d jk
d ij ( dijk) dEk
i Ek d El
El
or in integrated form
ij d ijk ijkl E l
Ek ,
(7.30)
which is the same as Eq. (7.3). Here, dijk are the converse piezoelectric moduli or the rstorder elec
trostrictive moduli, and Gijkl are secondorder electrostrictive moduli. In conformable matrix form,
^
q. (7.30) is given by Ed E L(EE c ), where (EE c ) is the selfconjugate (dyadic) product of electric
elds. In expanded matrix form, the strain matrix of Eq. (7.30) becomes
1 d 11 d 21 d 31 11 12 13 14 15 16 E E
1 1
d d 22 d 32 22 23 24 25 26 E2 E 2
2 12 E 21
3 d 13 d 23 d 33 1 31 32 33 34 35 36 E3 E 3
E
4 d 14 d 24 d 34 2 41 42 43 44 45 46 E2 E 3
E
d 15 d 25 d 35 3
51 52 53 54 55 56 E3 E 1
5
6
d 16 d 26 d 36
61 62 63 64 65 66
E1 E 2
(7.31)
called the electrooptical effect. Similar effects are obtained by the application of other external elds
such as magnetic, stress, and temperature changes. The corresponding effects are referred to as
magnetooptical, piezooptical, and thermooptical effects, respectively.
There are several ways to phenomenologically develop the previously mentioned optical ef
fects. For example, we could expand the relative permittivity tensor, Kij in a power series as a func
tion of electric eld E, magnetic eld H, and stress S. Two of the coefcients resulting from this
expansion would be called the electrooptical and piezooptical coefcients. Alternatively, we could
expand the electric eld strength E as a function of the polarization P, magnetic ux density B, and
strain E,thereby obtaining the electrooptical, magnetooptical, and elastooptical coefcients, and
so forth, the choice being arbitrary and a matter of convenience.
For our purposes, we will choose as the dependent variable the dielectric impermeability tensor
dened as
( )
Bij = K i1j = 0 Ei / Dj = Bji , (7.32)
m m m
where Dj is the electric ux density given vectorially as D K0E P . The refractive index of a crystal
is specied generally by an ellipsoid called the indicatrix whose coefcients at optical frequencies are
the components of the dielectric impermeability tensor Bij given by Bijxixj 1.
Expansion of the dielectric impermeability in a Taylors series about the state of a reference
temperature T 0, zero electric eld, zero magnetic ux density, and zero stress yields
1
n
Bij ( T , Ek , Bl , mn ) (T T 0 ) Ek Bl mn 0
Bij (T , 0 , 0 ,0 )
n 0 n !
T
E k
B l
mn
1 Bij Bij 2 B ij 2B ij
2 2
+ ( T )2
+ E E k o B B l p mn qr
E E + B B +
2 ! T 2 k o l p mn qr
B ij Bij B ij Bij
2 2 2 2
+2 Ek T + 2 T B Bl T + 2 T mn T + 2 E B Ek Bl
T Ek l mn k l
Bij
2
Bij
2
+2 E + 2 Bl mn + .
Ekmn Bl mn
k mn
(7.34)
SECOND AND HIGHERORDER EFFECTSSYMMETRY CONSIDERATIONS 131
Here, Bij (T 0,0,0,0) and all coefcients (in parentheses) are evaluated at a reference temperature T 0
and at zero electric eld, zero magnetic eld, and zero stress. We now develop phenomenologically
the 14 linear and quadratic optical effects expressed in Eq. (7.34).
Bij
T tij linear thermooptical effect
(T 0,0 ,0 ,0 )
2Bij
1
2 T 2 T j quadratic thermooptical effect
(T 0,0 ,0 ,0 ) i
Bij
E rijk linear electrooptical effect
k (T 0,0 ,0 ,0 )
1
2Bij
2 E E Rijko quadratic electrooptical (Kerr) effect
k o (T 0,0 ,0 ,0 )
Bij
B fijl linear magnetooptical (Faraday) effect
l (T 0,0 ,0 ,0 )
2Bij
1
2 Fijlp quadratic magnetooptical (CottonMouton) effect
Bl Bp (T 0,0 ,0 ,0 )
Bij
ijmn linear piezooptical effect
mn (T 0,0 ,0 ,0 )
2Bij
1
2 ijmnqr quadratic piezooptical effect
mn qr
(T 0,0 ,0 ,0 )
2Bij
T E ri(T
jk
)
thermoelectrooptical effect
k (T 0,0 ,0 ,0 )
2Bij
T B f jl(T ) thermomagnetooptical effect
i
l (T 0,0 ,0 ,0 )
2Bij
T
i(Tjmn) thermopiezooptical effect
mn (T 0,0 ,0 ,0 )
132 TENSOR PROPERTIES OF SOLIDS
2Bij
E B mijkl magnetoelectrooptical effect
k l
(T 0,0 ,0 ,0 )
2Bij
E zijkmn piezoelectrooptical effect
k mn
(T 0,0 ,0 ,0 )
2Bij
B wijlmn piezomagnetooptical effect.
l mn
(T 0,0 ,0 ,0 )
Only a few of these effects have been experimentally investigated and their tensor rank and sym
metry considered. In what follows, we will briey examine a few of the more common effects.
Bij Bij
2
or
In simplied notation, Eq. (7.37) can be expressed as $Br E or simply as $Br^ E in conformable
matrix form. Thus, the matrix representation of Eq. (7.37) is the same as the converse piezoelectric
effect given by Eq. (6.11). with E replaced by $B and d replaced by r. Because rijk and dijk are both
thirdrank polar tensors, the symmetry restrictions on their coefcients must be the same. Thus, rijk 0
for all 11 centrosymmetrical crystal classes and the rmk for the linear electrooptical moduli are the
same as those in Table 6.2 if the transpose of each array is taken with the subscripts mk reversed as in
Eqs. (6.10) and (6.11). Remember that the d moduli arrays in Table 6.2 are given in normal form.
SECOND AND HIGHERORDER EFFECTSSYMMETRY CONSIDERATIONS 133
Because the linear electrooptical effect is possible only in piezoelectric crystals, the presence
of an externally applied electric eld will produce a slight change in the shape of the crystal by the
converse piezoelectric effect. The change in crystal shape results in the elastooptical effect, to be
considered in Section 7.3.2. As a result, the electrooptical effect will consist of two components:
1) the true (primary) linear electrooptical effect and 2) the false (secondary) linear electrooptical
effect. Combined, these effects are given by
or
Bm Rmn En2 (m, n = 1 6), and Rmn Rnm . (7.41)
B1 R 11 R 12 R 13 R 14 R 15 R 16 E1 E 1
B R R 22 R 23 R 24 R 25 R 26 E2 E 2
2 21
B3 R 31 R 32 R 33 R 34 R 35 R 36 E3 E 3
. .
B4 R 41 R 42 R 43 R44 R 45 R 46 E2 E 3
B5 R 51 R 52 R 53 R 54 R 55 R 56 E3 E 1
B6 R 61 R 62 R 63 R 64 R 65 R66 E1 E 2 (7.42)
134 TENSOR PROPERTIES OF SOLIDS
Here, the Rmn coefcients are related to the Rijko coefcients by the rules: Rmn Rijko if n1
3,
and Rmn 2Rijko if n4
6. The restrictions imposed by crystal symmetry on the coefcients
Rmn are exactly the same as those imposed on the linear piezooptical coefcients considered in
Section 7.3.2.
As in the case of the linear electrooptical effect, the quadratic effect will normally contain
two parts: 1) the true (primary) quadratic electrooptical effect and 2) the false (secondary) qua
dratic electrooptical effect. This can be expressed as
where Rijko
* are the coefcients for the true quadratic electrooptical effect and pijlm are the compo
nents for the elastooptical effect. Equation (7.43) can be cast into an alternative form by use of sec
ondorder electrostrictive coefcients given in Eq. (7.4). When this is done, Eq. (7.43) becomes
Bij ( Rijko pijlm lmko )Ek Eo ,
(7.44)
where now the pG product appears as a correction to the true quadratic electrooptical (Kerr) effect.
The pG correction factor is usually weak but can become important in some ferroelectric crystals.
Bij 2Bij
mnqr
1
Bij (mn ) Bij ( 0) 2
mn
mn mnqr
or
B1 11 12 13 14 15 16 1
B
22 23 24 25 26
2
2
21
B3
31 32 33 34 35 36
3
.
,
B4
41 42 43 44 45 46
4
B5
51 52 53 54 55 56
5
B6
61 62 63 64 65 66
6 (7.47)
The elastooptical coefcients can be obtained in a similar manner by expressing the imper
meability tensor as functions of the strain components of the crystal, as in Eq. (7.43), to give
Now, Pop Pijlm for all o and p with no factors of 2 or 1 2 present. The elastooptical and piezo
optical coefcients are related through the elastic moduli c and s, respectively, by the equations
B q Bo p
pop = o = oq cqp and oq pop spq . (7.50)
q p
p
q
The effect of crystal symmetry on the piezooptical coefcients Poq can be determined by ap
plying the direct inspection method to all crystal classes except the trigonal and hexagonal systems
for which the bruteforce method must be used. Thus, for the trigonal and hexagonal systems, the
transformation equation must be used:
which also applies to the quadratic electrooptical coefcients R given in Eq. (7.42). Note that Eq. (7.51)
derives from B aABAPSAPA1SaPaSa because BPS applies to the old axes 0xi , whereas
B aPaSa applies to the new axes 0xia. Here, the linear quadratic electrooptical coefcients Rmn will
be affected by crystal symmetry exactly as will be Pmn . Shown in Table 7.1 are the piezooptical coef
cients Pmn for the seven crystal systems and the isotropic solid with the understanding that PijxPji.
This table can also be applied to the elastooptical coefcients with some minor changes.
136 TENSOR PROPERTIES OF SOLIDS
B1 B1 B 0 11 12 12 0 0 0 1
B B B 0 11 12 0 0 0 2
2 2 12
B3 B3 B 0 12 12 11 0 0 0 3
. ,
B4 B4 0 0 0 44 0 0 4
B5 B 0 0 0 0 44 0 5
5
B6
B6
0 0 0 0 0 44
6 (7.52)
where B 0 is the reference dielectric impermeability dened by the indicatrix sphere for the unde
formed crystal in the absence of temperature, electric, and magnetic elds
x2 x2 x2
B 0 ( x12 + x22 + x32 ) = 01 2 + 02 2 + 03 2 = 1 (7.53)
(n ) (n ) (n )
because B 0 1(n0)2. Here, n0 is the refractive index in the absence of all external elds.
Now, let a uniaxial tensile stress S2 be applied along the 0x2 direction, with 0x1 and 0x3 being
the other cubic unit cell axes. Because $B4$B5$B60, Eq. (7.52) reduces to
B1 122
B2 11 2
B 3 12 2 . (7.54)
The changes in the three principal refractive indices can be determined by noting, for example, that
Bi 1 / ni2. Then, after differentiation, there results $Bi
(2 / ni3 )$ni Bi Bi0 Bi0 along the prin
cipal axes. Thus, n n0, which gives the change in the three principal refractive indices as
1 1
n1 (n0 )3 B1 (n 0 )3 122
2 2
1 1
n2 (n0 )3 B2 (n0 )3 11 2
2 2
1 0 3 1 03
n3 (n ) B3 (n ) 12 2 . (7.55)
2 2
This shows that $n1 $n3 and that the crystal has become uniaxial. Therefore, for light traveling
along x2, the birefringence (also called double refraction) is zero because $n1 $n3. However, for
light traveling along either x1 or x3, the birefringence becomes
SECOND AND HIGHERORDER EFFECTSSYMMETRY CONSIDERATIONS 137
TABLE 7.1: The independent piezooptical coefcients Pmn and quadratic electrooptical coefcients
Rmn are identical for the seven crystal systems and the isotropic solid
Triclinic
1,
Monoclinic
Orthorhombic
2mm, 222, mmm
138 TENSOR PROPERTIES OF SOLIDS
Trigonal
3,   3m, 32, 3 m
Hexagonal
6, 6 , 6 / m 6mm, 622, 6 m, 6 / mmm
Isotropic
To obtain p coefcients, multiply the *P coefcient entries by , all others directly convertible. The classes to which each coefcient
array belongs is indicated above each array. The coefcient arrays for the elastooptical coefcients pmn are obtained by replacing
P by p except as indicated by an asterisk *.
giving the difference between the refractive index parallel and perpendicular to the stress direction.
A similar uniaxial tensile stress analysis on a cubic crystal class 23 or m3 will show that the crystal
becomes biaxial. In short, a cubic crystal becomes optically uniaxial if a tensile stress is applied along
any cubic axis but is optically biaxial if a uniaxial tensile stress is applied along any other axis (see
Nye in Endnotes for a indepth treatment of double refraction).
be divided into symmetrical and antisymmetrical parts, BijS and BijA , as in Eqs. (2.16), (2.17), and
(2.18), respectively. Thus,
and
By denition, BijS (B) is an even function of the magnetic ux density B, whereas BijA (B) is an odd
function of B. Given this, the quadratic magnetooptical effect can be obtained by expanding
the symmetrical part of the dielectric impermeability BijS in a Taylors series as an even func
tion of a small externally applied magnetic ux density B about the state of a reference tem
perature T 0 and zero electric eld and zero stress. Thus, the expansion yields coefcients for n
0,2,4, ... in Eq. (2.52), with the result,
1 Bij
2 S
BiSj (Bk ,Bl ) = BiSj (0, 0) + B B +
2 Bk Bl k l (7.60)
or
BSij Fijkl BkBl ,
(7.61)
where
1 Bij
2 S
Fijkl =
2 Bk Bl (7.62)
as dened earlier in Section 7.3. Here,Fijkl is a polar, nonmagnetic, fourthrank tensor property
representing the coefcients for the quadratic magnetooptical effect known as the CottonMouton
effect.
Because there is symmetry in both Bij and the dyadic product BkBl , Eq. (7.61) can be cast in
the form
for which B12B1B1, B22B2B2, B32B3B3, B42B2B3, B52B3B1, and B62B1B2. Now, the Fmn coef
cients are related to the Fijkl coefcients by the rules
Fmn Fijkl if n 1, 2, or 3
Fmn 2Fijkl if n 4, 5, or 6.
The effects of crystal symmetry on the Fmn coefcients are exactly the same as those imposed on the
piezooptical coefcients Pmn given in Table 7.1 obtained by replacing P with F.
Qualitatively, the CottonMouton effect can be explained in the following way. When a dielec
tric is placed in a magnetic eld, it may undergo a phase difference or retardation between the velocity
of the ordinary light wave and that of the extraordinary light wave. This retardation is proportional to
the square of the magnetic ux density B, the difference between CottonMouton moduli, and cube
of the refractive index n0. Thus, the phase difference is directly related to the dielectric impermeability
tensor via Eq. (7.61) (for a further discussion, see Landau and Lifshitz in Endnotes).
The antisymmetrical part of Bij, labeled BijA, can be expanded in a Taylors series as an odd
function of a small B eld about the state of a reference temperature T 0 and zero electric eld and
stress. This leads to the linear magnetooptical effect expressed as
BA
BiAj (Bk ) = BiAj ( 0 ) + ij Bk + ,
Bk (7.64)
where
BiAj
B fijk , (7.65)
k
Here, fijk represents the linear magnetooptical effect known as the Faraday effect. Because BijA is an
antisymmetrical, magnetic, secondrank tensor and Bk is an axial magnetic vector, then fijk must be
an axial, antisymmetrical (in i and j), nonmagnetic tensor of rank three such that
where Gl is the axialmagnetic vector corresponding to the antisymmetrical magnetic tensor $BijA .
This allows Eq. (7.67) to be presented in the form
which results from multiplying both sides of Eq. (7.67) by elij since the value ee^ 2tr(ee) 6.
Here, flk 1/6elijfijk is a polar, nonmagnetic secondrank tensor for which flk xfkl and is called the
Faraday tensor. Thus, the thirdrank, axial, antisymmetrical Faraday tensor fijk is related to the polar,
asymmetrical, secondrank Faraday tensor flk via the permutation tensor elij. The effect of crystal
symmetry on flk can be found by applying the transformation law f aaf a^ to each crystal class.
When this is done, the results are identical to those for the Seebeck effect in Table 9.1 as discussed
in Section 9.1.
Qualitatively, the Faraday effect can be explained as follows: When a transparent isotropic
magnetic material is subjected to a DC magnetic eld and linear polarized light travels parallel or
antiparallel to that magnetic eld, the plane of polarization is rotated. The angle of rotation is called
the Faraday rotation angle found to be proportional to the magnetic eld strength, the thickness of
the transparent medium along the optic axis, and the Faraday tensor considered to be a Hermitian
tensor. In tensor notation, the Faraday rotation angle is given by
along the optic axis say x3 and where BiMik Hk, or for an isotropic material BMH. Here, V(W is
called the Verdet coefcient, which is a function of the frequency W of the light wave. Further discus
sion of the Faraday effect is beyond the scope of this text and is left for further study by the reader
(see Newnham in Endnotes for additional reading on the subject).
Bij Bij
Bij (T ) = Bij (T 0 ) + T + or Bij T tij T (7.70)
T T
where tij is the symmetrical, secondrank, linear thermooptical property tensor that is affected by
crystal symmetry according to Table 3.7.
SECOND AND HIGHERORDER EFFECTSSYMMETRY CONSIDERATIONS 143
Because the change in temperature of a crystal produces a thermal expansion, tij contains a
false (secondary) thermooptical part in addition to the true (primary) part. The two contributions
can be expressed as
Bij
tij = tij + kl = tij + pijkl kl = ttrue + tfalse . (7.71)
kl T
Here, pa and A represent the photoelastic and thermal expansion coefcients, respectively. The effect
of crystal symmetry on the pa coefcients is the same as the elastooptical coefcients p obtained
from Table 7.1 (see Newnham in Endnotes for additional reading on the subject).
In addition to the linear thermooptical effect, there also exists the quadratic thermo
optical effect dened in Section 7.3. This effect can be obtained from the continued expansion of
Eq. (7.70) given by
Bij 2 B ij
Bij (T ) = Bij (T 0) + T + 12 2
T 2 +
T T
or
Bij 2 Bij
Bij T 2
1
2T 2 tij T Tij T 2 . (7.72)
T
T
The contribution of the Tij $T 2 term to the total thermooptical effect will be, in most cases, negli
gible compared with the linear thermooptical effect that will be present.
145
P A R T II
CHAPTER 8
Up to this point, we have concerned ourselves only with equilibrium properties, meaning those that
are thermodynamically reversible. We now undertake the considerable task of presenting the concepts
of irreversible thermodynamics that are fundamental to the general understanding of the transport
properties. To do this will require a somewhat less tangible treatment than was used to discuss the
equilibrium properties in Part I. However, every effort will be made to provide a lucid stepbystep
presentation of the more complex concepts fundamental to irreversible thermodynamics.
r r r
grad i j k
, (8.1)
x1 x2 x3
m m m
where i , j , and k are the unit vectors along Cartesian axes x1, x2, and x3, respectively. The Fas are
scalar eld potentials representing electrostatic potential E, temperature T, and mass concentration
C (not to be confused with the symbol C for coulombs). A potential gradient is assumed to be from
low to high potential (or concentration). In the case of electrostatic potential gradient, we used the
m
convention that high potential is more positive than low potential. The ux vectors J A represent
the ow of number of positive test charges n, heat q, and mass m all per square meter per second
(m2/s). A positive test charge is taken to be the charge magnitude on an electron but taken as posi
tive, hence, \e \.
148 TENSOR PROPERTIES OF SOLIDS
TABLE 8.1: Forceux (causeeffect) vector parameters and dimensions in SI units for the ow
of electric current, heat, and mass
m
Gradient or afnity FB Current density (ux), (effect) JA
Note that SI units are used for the forces and uxes.
The principal steadystate properties relating cause and effect are given, generally, in tensor
subscript notation by
Ji Ki
j
j (8.2)
or
J K . F (8.3)
as the single contraction product in vector notation. The minus sign is used to express ow from
high to low potential (or from high to low concentration), with FB being the driving force. Thus,
if a concentration increases in, say, the x direction, then the ow must be in the opposite (x direc
tion). In the case of electric current ux, we take positive current ow from high to low electrostatic
potential. These facts must be kept in mind as we progress through the remainder of this chapter.
We represent [KijAB] as the matrix of conductivities Kij , each of which is a secondrank ten
sor property. In expanded matrix form and in the absence of a magnetic eld, the three equations
representing Eq. (8.2) are given by
J ni KinE
j
KinT
j
KinC
j
j E
q qE T
J i Kij KiqT
j
KiqC
j j
J mi KimE KimT mC
Kij
j C (8.4)
j j
where, in general, KijAB x KijBA, meaning that the matrix [KijAB] is not symmetrical. We may take the
inversion of Eq. (8.2) to express the matrix of resistivities given by
i (Ki
j
)1 Jj i
j
Jj (8.5)
where, in general, RijAB x RijBA and where R K
1. Note that the superscripts in Eqs. (8.2) to (8.5) are
for identication purposes only.
J in
KinE
j
j FE or ji Sij Ej (inverse Ohms law), (8.6)
where Sij is given in units of (7. m)1 (mho/m) and KijnE in units of (m. s . V)1, consis
tent with Table 8.1. Note that Ei Rij jj represents generalized Ohms law where Rij is the
resistivity tensor in units of (7. m). It is an accepted common use that Ej
jFE as will
be the case in this test.
2. Thermal conductivity: KijqT or kij under condition J n 0
J iq
KiqT
j
jFT or hi
kij j T (Fouriers law), (8.7)
where KijqT and kij are given in units of ( J/s/m K) (W/m K), consistent with Table 8.1.
3. Diffusivity: KijmC or Dij
J im
KimC
j
j FC or J im
Dij j C (Ficks law), (8.8)
where KijmC and Dij are given in units of (m2/s), consistent with Table 8.1.
The fact that (K AB) and (K BA) do not produce symmetrical coefcients is not surprising.
Recall that for the equilibrium compliances Cmn and rigidities Rmn, the products of the conjugate
parameters (Ii )(ei ) all have dimensions of energy density (energy per unit volume), which allowed,
with help of Greens theorem, Cmn Cnm and Rmn Rnm as indicated in Section 4.4. An inspection of
Table 8.2 makes it clear that the conjugate parameters ( J A)(FA) have no consistent dimensions.
Even if all ( J A)(FA) products had the dimensions of energy or energy density, it is not clear
at this point what the criterion would be for the symmetry KijAB KijBA. The following sections estab
lish this criterion and the general method of representing properties of irreversible processes.
1 1
Ji = Lij Xj + Lijk Xj Xk + Lijkl Xj Xk Xl + ..., (8.9)
2! 3!
where Lij (uJi /uXj )X0 and Lijk (u2Ji /uXj uXk )X0 are the kinetic coefcients and secondorder
kinetic coefcients, respectively, and so forth.
Because the applied afnities are usually very small, a truncated form of the power series of
Eq. (8.9) gives to a very good approximation the phenomenological relation
TRANSPORT PROPERTIES AND IRREVERSIBLE THERMODYNAMICS 151
which represents a linear Markoff process. Here, JiA and XjB are the uxes and driving forces (af
nities), respectively. The LijAB are the phenomenological coefcients that are related to the conduc
tivities KijAB but will not, in general, be identical to them. This relationship may be classied by the
following:
LAA Related to the conjugate or proper conductivities S,k, D
LAB(AxB) Related to the cross or interference conductivities as, for example, thermoelectric,
electrodiffusive, and thermodiffusive coefcients.
For a system in thermodynamic equilibrium, every type of micromotion occurs just as often as
its reverse.
Using uctuation theory for the small spontaneous motions around thermodynamic equilibrium,
Onsager (after Lars Onsager, 19031976) proved what is now referred to as Onsagers principle.
Provided a proper choice is made for the uxes Ji and driving forces (afnities) Xj , the matrix
of phenomenological coefcients (Lij ) is symmetrical, that is
LiAB
j
LjBA
i
and LiAA
j
LjAA
i
(i, j 1, 2,...n), (8.11)
but LiAB
j
LjAB
i
.
The relationships, Eqs. (8.11), are called Onsagers reciprocal relations in the absence of a magnetic
eld. Note that only the LAA phenomenological coefcients have self symmetry in the sense of
LijAA LjiAA.
In a magnetic eld, the reciprocal relations for LAB that are even functions of H must be
modied according to
m m m m
LiAB
j
(H ) LjBA
i
(
H ) and LiAA
j
(H ) LjAA
i
(
H ) (i, j 1, 2,...n), (8.12)
152 TENSOR PROPERTIES OF SOLIDS
m m
which means that LijAB is the same function of (H ) as LjiBA is of (
H ). Similarly, LijAA is the same func
m m
tion of (H ) as LjiAA is of (
H ). These results have their origin in the Lorentz force vector given by
m m m m m
F e(v s B ), where e and v are the charge and velocity vector of a particle, respectively, B is the
m m m m
magnetic ux density vector, and v s B indicates the cross product between v and B . The recipro
cal relations require that both the velocity and magnetic eld strength be reversed to ensure that all
particles retrace their former paths. The LijAB coefcients that are odd functions of the magnetic eld
will be discussed in Section 10.1.
where l is length (e.g., meter, m), t is time (e.g., second, s), and T is temperature (e.g., K) as in the
SI system of units for which energy is given in joules, (1 W 1 J/s). Thus, we take entropy density
production as the time variation of unrecoverable work per unit volume per unit temperature inside
the system and whose quadratic form must be positive denite. In general, we assert the require
ments that
s. 0 (reversible process)
s. 0 (irreversible process)
s. 0 (a process that cannot occur without altering the system conditions).
where J e is the charged electron ux in the direction of the electrostatic potential gradient.
The afnity (force) is given by
X 1 i
T
i
T
(in units of Energy/lT ),
where
M Mc eF (8.14)
is the electrochemical potential (total energy per particle, also called the Fermi level in the
equilibrium state), Mc is the chemical potential per particle, eF is the electrostatic potential
per particle, and e is the charge on the particle assumed to be a positive test charge equal to
\e \ 1.60 s 10
19 C. Thus, the inner product of the conjugate parameters for the ow of
electronic charge gives the entropy density production per particle as
(
s J ni i ( T
(in units of Energy/l 3tT ), (8.15)
which will later be shown to satisfy the corresponding reciprocity relations. Be aware of the
fact that we are using the positive current convention and that high electrostatic potential
is more positive than low electrostatic potential. Thus, Jin is always in a direction counter to
the electrostatic potential gradient, which is from low potential to high potential.
2. Flow of entropy or heat:
The inner product of the conjugate parameters for the ow of entropy yields the entropy
production as
(
s J si T i ( 1 3
T (in units of Energy/l tT ), (8.16)
which will be shown to satisfy the corresponding reciprocity relations. Alternatively, for our
purpose, because J q T J s, the conjugate parameters become
Combining Eqs. (8.15), (8.17), and (8.18) yields the total entropy density production for all
three processes as
Xi Jin i
J q 1
J m c
,
s i Ji
i i
(8.19)
T T i i T
which are each represented in units of Energy/l 3tT ). Thus, the phenomenological relations for the
three types of ow can be written in the following matrix forms
Jin Li11j Li12j Li13j j( T )
q
21
Ji
Lij Lij
22
Li23
j
j (1 T )
.
J m
L 31 L 32 Li33
T )
(8.20)
i ij ij j j c
Here, diagonal LijAA are the principal phenomenological coefcients and the LijAB are the cross or
interference coefcients. Onsagers reciprocity theorem permits the following relationships between
the phenomenological coefcients in the absence of a magnetic eld
~ ~
LiBA
j
LjAB
i
or LBA LAB for A x B but LBA x LAB, that is, LijAB x LjAB
i
and
~
LiAA
j
LjAA
i
or LAA LAA for AB.
TRANSPORT PROPERTIES AND IRREVERSIBLE THERMODYNAMICS 155
J1n L1111 11
L12 11
L31 12
L11 12
L12 L12
13
1 ( )
T
n
11
J2
L12
11
L22 11
L23 12
L21 L12
22
L12
23
2
( )
T
J n
q3
L11
31
11
L23 11
L33 12
L31 12
L32 12
L33
3 1
( )
,
T
J1
L1211
12
L21 12
L31 L22
11
22
L12 L31
1 ( T)
22
Jq
L12 12
L22 12
L32 22
L12 22
L22 22
L23 ( 1 T)
2
12
2 1
3 ( T )
q 12 12 12 22 22 22
J3
L13 L23 L33 L31 L23 L33 (8.21)
11 11 22 22 21 12 12 12
where L L , L L , and L L , meaning that Lij21 Lji12, but L x L .
s L
X X 0, (8.22)
which is positive denite and implies that the matrix of phenomenological coefcients LAB also be
positive denite. For this to be so requires that that determinant of the LAB matrix and all of its mi
nors be positive denite. Take, for example, a twoow process involving a twodimensional matrix
LAB given by
12 21
where L L according to Onsagers principle. The necessary and sufcient condition for Eq. (8.23)
to be positive denite is that the 2 s 2 determinant of LAB be positive denite. Thus,
L11 L12
= L11 L22 (L12) 2 > 0. (8.24)
21 22
L L
Generally, the diagonal coefcients LAA 0 (i.e., are positive), but the LAB coefcients can be
positive or negative. Applying Eq. (8.13) to the ow of electric charge and heat given in Eq. (8.20),
we would write the entropy production for any twoow process as
156 TENSOR PROPERTIES OF SOLIDS
s L
(
X X L X X 2 L X X L X X ) 0 (8.25)
which must be valid if the LAB matrix is to obey Onsagers reciprocal relations L12L21. Note that
L11L22 and (L12)2 both have units of T 2(l . t)
2 for the ow of electric charge and heat.
(
Jiq Lj12i j Li22
T j
j ( 1
T (8.29)
The phenomenological coefcients Lij in Eqs. (8.28) and (8.29) can now be related to the
familiar conductivities Sij and kij. We begin with the electrical conductivity Sij , which is dened as
the electric current density
eJin per unit potential gradient F M
/e in an isothermal system, the
latter being essentially an electromotive force because Mc 0, giving M
e F. Therefore, under
isothermal conditions, Eq. (8.28) becomes
(
Jin Li11j ( 1 11
T j eLij
j
T
for T 0
TRANSPORT PROPERTIES AND IRREVERSIBLE THERMODYNAMICS 157
and
eJin
ij e 2 Li11j / T ji , (8.30)
j
which indicates symmetry of the electrical conductivity, Sij Sji because Lij11 Lji11 . Thus, the electri
cal conductivity is a symmetrical secondrank tensor with the component array given by Eq. (2.17).
Solving for Lij11 in Eq. (8.30) gives
Li11
j
TSij /e 2. (8.31)
Next, we turn to the heat conductivity dened as the heat current density per unit temperature
gradient for zero electric current, J n 0. For this purpose, Eqs. (8.28) and (8.29) become
0 Li11 j
L12 j T (8.32)
j
T ij
T 2
and
Jiq Lj12 j
L22 j T
. (8.33)
i ij j 2
T
T
Solving for j in Eq. (8.32) gives, with subscripts excluded for simplicity,
T
( 11)1 12 T
L L , for J n 0
T T 2
which when substituted into Eq. (8.33) yields
(
Jq ~L 12
(L11)1 L12 L22
( T
T2 . (8.34)
The thermal conductivity tensor, dened as the heat current density
Jiq per unit temperature
gradient jT, now becomes
~
where by Eq. (8.11) Lji12 Lij12 L12, and \DL \ 0 is the determinant of the phenomenological coef
~
cients. Here, (L12)2 is a symmetrical square matrix often represented as L12L12 in matrix symbology.
Because L11, L22, and (L12)2 are all symmetrical square matrices, we are permitted to state that
We can now write Eqs. (8.28) and (8.29) in terms of the conductivities Sij and kij by introduc
ing the expressions for Lij11 and Lij22 in Eqs. (8.31) and (8.37) with the results
T ij (
Jin
e
2
j
T
12
Lij
j
1
T ( (8.38)
T 2 k e (L12)2 ( ) 1 1 ,
(
(
2
j
Jiq L12
(8.39)
ji
T
ij T ij j T
~
where (L12)2 Lji12Lij12 L12L12. Equations (8.38) and (8.39) give the generalized forceux expres
sions for the dual ows of electricity and heat in an anisotropic solid both in terms of the conduc
tivities Sij and kij and the crosscoupled phenomenological coefcient Lij12 yet to be determined in
Section 9.1. By dropping the subscripts i and j, these equations can be applied to the onedimensional
ow of electricity and heat in a homogeneous isotropic wire or rod.
We end this section by dening thermal resistivity tensor rij as the inverse of the thermal
conductivity tensor. Following Eq. (2.35), the inverse of kij is rij given by
i T
rij (8.40)
Jjq
or in matrix notation r k
1.
( 1)(i + j )Mji 
( kij ) 1 = = r i j = r ji , (8.41)
 kij 
where \Mji \ is the ji th minor of \kij \, indicating that any individual component of rij is not the simple
reciprocal of kij component. The same reasoning applies to the relationship between the electrical
conductivity Sij and resistivity Rij expressed by (Sij)
1 Rij .
159
CHAPTER 9
Thermoelectric, Piezothermoelectric,
and Diffusive Effects in Solids
In previous sections, we dealt mainly with the conduction of electricity and heat as two separate
processes. This was done to formalize the conductivity denitions and dene the phenomenological
coefcients Lij11 and Lij22 in terms of the proper conductivities Sij and kij . Now we will consider the
simultaneous ow of electricity and heat usually referred to as the thermoelectric effects or, more
specically, the Seebeck, Peltier, and Thomson effects. In doing this, we will recognize that the ir
reversible processes involved interfere with one another. Thus, we will have to take into account the
cross coupled or interference effects by making use of the developments given in Section 8.4. To
simplify the treatment given here, we will begin with the isotropic case and then move to the gen
eralized case of the anisotropic solids. In fact, it will be instructive to switch back and forth between
the isotropic and anisotropic nomenclature as needed.
TL (3) T0 (2) TH
B B
(4) (1)
= 1 4
FIGURE 9.1: Thermocouple setup showing two dissimilar metals A and B joined at junctions that are
maintained at different temperature TH and TL.
Figure 9.1, there can be no temperature gradient across the open circuit of the ideal capacitor. Thus,
the absolute thermoelectric power must be dened as the change in electrostatic voltage potential
per unit change in temperature relative to the heat reservoirs. Thus, by using Eqs. (9.1) and (8.31),
we have
12 12
L eL
in units of (V/K) (9.2)
11 2
T eTL T
in terms of L12 and S. Solving for L12 then gives the result
T 2
L12 . (9.3)
e
From Figure 9.1, because there is no temperature gradient across the capacitor held at tem
perature T 0, we can sum the electrostatic potential differences as
Therefore, the resulting absolute thermoelectric power for the thermocouple becomes
AB L12 L12
AB A 11 B
A B
(9.4)
T eTLA
11
eTLB
By introducing Eq. (9.3) into Eqs. (8.38) and (8.39), we can cast these thermoelectric equa
tions into forms containing physically measurable quantities (S, k, and ) as they apply to a ther
moelectric junction composed of two different isotropic conductors. When this is done, the results
are, excluding subscripts,
T
T 2
(
Jn 2
e
T
e 1
T ( (9.6)
T2 (
Jq
e
T
T 2 k T 2
1
T
.
( (9.7)
Then, by eliminating
between Eqs. (9.6) and (9.7), there results
T
e2 J n e
T . (9.8)
T T T
Finally, by introducing Eq. (9.8) into Eq. (9.7) with (1/T ) =
T /T 2 and with a little alge
bra, Eq. (9.7) can be written in the useful alternative form
J q eT J n kT TJ s (9.9)
, (9.10)
eT J n T 0 J e T 0
where J n
J e /e and J q T J s.
TABLE 9.1: Effect of crystal symmetry on ij for the tetragonal, trigonal, and
hexagonal systems, all others being the same as in Table 3.7 except that ij x ji
CLASSES CLASSES
4, 4 , \\4/m \\, 3, \\3 \\ 4mm, 4 2m, 422, \\4/mmm \\, 3m, 32, \\3 m \\
6, 6 , \\6/m \\ \\
6 m2 \\, 6mm, 622, \\6 /mmm \\
To apply Eqs. (9.6) and (9.7) to an anisotropic solid, one need only reinstall the subscripts
and take into account the affect of crystal symmetry on the property tensorsall of which are
secondrank tensors but only ij is nonsymmetrical.
The effect of crystal symmetry on the ij components follows Table 3.7 for Sij with the fol
lowing changes: 1) crystal systems are the same as Sij except that ij x ji and 2) the uniaxial group
of tetragonal, trigonal, and hexagonal systems is given as in Table 9.1.
J q eT J n TJ s . (9.11)
Heat evolved
(J q)A > (J q)B
Constant T
junction
Jn
A B
(J q)A (J q)B
By denition, the Peltier coefcient is the heat that must be removed from the isothermal
junction AB per unit electric current ux from conductor A to conductor B as depicted in Figure 9.2.
This is expressed by
J Bq JAq
AB
T AB , (9.13)
n
eJ T 0
giving the relationship between the Peltier and Seebeck (thermoelectric power) coefcients.
Equation (9.13) is known as the rst Kelvin relation. Thus, if ( J Aq
J Bq ) 0, heat must be issued from
the isothermal junction AB to the surroundings (thermoelectric heating). Or if ( J Aq
J Bq ) 0, heat
must be supplied to (absorbed by) the isothermal junction from the surroundings (thermoelectric
cooling) as illustrated in Figure 9.2.
In tensor notation, applicable to anisotropic crystals, the Peltier and Seebeck coefcients are
related according to
ij T ij x ji since ij x ji , (9.14)
where the effect of crystal symmetry for ij is the same as that for ij given in Table 9.1. It should
be noted that the developments presented by Eqs. (9.11), (9.12), and (9.13) apply to homogeneous
isotropic conducting materials.
Thomson
Heat
Heat Reservoir
TT
Jn Jn'
Jq T J q'
x
Heat Reservoir
Thomson
Heat
FIGURE 9.3: Schematic illustrating the Thomson effect in a homogenous rod element $x of a constant
cross section carrying heat and electric currents and surrounded by heat reservoirs.
164 TENSOR PROPERTIES OF SOLIDS
to maintain the steady temperature distribution. This is what is called the Thomson effect (after Sir
William Thomson, who later became Lord Kelvin), and the heat that is exchanged in this process
is called the Thomson heat as depicted by the closed system in Figure 9.3. Whether the Thomson
heat is emitted to or absorbed from the surroundings depends on the direction and magnitude of
the electric current relative to the heat ow.
We now establish an energy ow balance given by uxes
where the substitution property of the Kronecker delta Dji has been used (see Section 2.6.3). The rate
at which energy is interchanged between the rod element and the surroundings in Figure 9.3 is the
divergence (Section 2.6.2) of Eq. (9.16) represented by
j T j
e 2J n 1 e T
i ji ji i (9.18)
T
or
1
e 2ji Jin (e jiiT ji i ) (9.19)
because Djii M
j M
.
Introducing Eq. (9.19) into Eq. (9.17) yields
where Sij
1 Rij and e 2Rji Jin Jjn is the Joule (I 2R) heat that is generated by current ow through a
conductor even in the absence of a temperature gradient. But for the steadystate conditions, J n 0
and . J n 0, it follows that . J u must vanish. If we set . J n 0 and . J u 0, we have
i ( k i T )
j j J n 0 0,
J u 0
THERMOELECTRIC, PIEZOTHERMOELECTRIC, AND DIFFUSIVE EFFECTS 165
We now note that the thermoelectric power ji is a function of the local temperature repre
sented as i ji / iT u ji / uT, which allows
ji
i j i T .
(9.22)
i
T
Here,
ji
ji T ij (9.24)
T
is the Thomson heat coefcient, which is seen to be an asymmetrical secondrank tensor where the
effect of crystal symmetry follows that for ji x ij in Table 9.1. Equation (9.24) is known as the
second Kelvin relation. Thus, the Thomson heat is the heat evolved or absorbed per unit volume
per unit time depending on the direction and magnitude of the current Jin relative to the Joule heat
it produces. The Thomson coefcient is usually (but not always) dened as positive if heat must be
added to (absorbed by) the element in Figure 9.3 so as to maintain the steadystate temperature
distribution in the element. Notice that the Thomson heat (proportional to J n) changes sign when
the current density is reversed but that the Joule heat does not because it is proportional to the
square of the current density.
The foregoing results apply generally to an anisotropic conducting material. However, they
can be applied to homogeneous isotropic conductors or semiconductors by dropping subscripts
except for a sufx indicating a specic direction along which the heat effects are generated. When
this is done, for example, Eq. (9.23) becomes
J u T e J n e 2 ( J n )2 . (9.25)
T homson heat Joule heat
166 TENSOR PROPERTIES OF SOLIDS
This single direction would apply to onedimensional ow in the longitudinal direction of the con
ducting rod (e.g., the x direction). In the isotropic case, the Thomson coefcient is given by the known
isotropic value for T when substituted for the S cubic (diagonal) values presented in Table 3.7.
n
1
ij (T , kl )
(T T0 ) kl ij (T0 , 0 )
n 0 n!
T kl
ij ij
ij (T0 , 0 )
( T T 0
)
kl
T ( T0 , 0 ) kl (T , 0)
0
2
1
ij 2 ij
( T T 0) 2
2 ( T T 0 ) kl
2!
T 2
T
( T0 , 0 ) kl ( T0 , 0 )
2 ij
kl op ,
(9.26)
kl op ( T0 , 0 )
where ij (T0, 0) and all coefcients (in parentheses) are evaluated at temperature T0 and zero
stress.
Assuming that all measurements are to be conducted at a reference temperature of T T0 and
that all second and higherorder terms in stress can be neglected, Eq. (9.26) becomes
ij ij (T0 , kl ) ij (T0 , 0 )
ij
kl ijkl kl
kl (T , 0) (9.27)
0
THERMOELECTRIC, PIEZOTHERMOELECTRIC, AND DIFFUSIVE EFFECTS 167
where ijkl is a fourthrank polar tensor called the piezothermoelectric power tensor, not to be confused
with the Peltier coefcient . Because Skl is symmetrical but $ij is not, then ijkl ijlk or
$i ij Sj (i 1 9; j 1 6) (9.28)
in matrix subscript notation. Thus ij in Eq. (9.28) is completely specied by 54 independent coef
cients for the triclinic crystal system given by
2
21
3
31 32 33 34 35 36
1
2
4
41 42 43 44 45 46
52 53 54 55 56
3
5
51
4
6
61 62 63 64 65 66
72 73 74 75 76
5
7
71
6
8
81 82 83 84 85 86
92 93 94 95 96
9 91 (9.29)
The transformation law for the piezothermoelectric power tensor is easily determined
from the transformation laws for stress and thermoelectric power. These transformation laws are
Sa AS or S A
1Sa, as given in Section 6.1.1, and is a B, where A is the quadratic transfor
mation form for symmetrical secondrank polar tensors and B is the general quadratic transforma
tion form for asymmetrical secondrank polar tensors. If a aSa relative to coordinate axes 0xa
and S relative to axes 0x, then it follows that
a B BS BA 1SaaSa
or
aBA 1 (9.30)
in matrix symbolic notation. The quadratic transformation form B is given by Eq. (9.31), where it
is divided into nine 3 s 3 submatrices (numbered in parentheses), 4 of which are replicated as indi
j
cated by the symbols j and . Eq. (9.31) can be deduced from that of A given by Eq. (2.22).
168 TENSOR PROPERTIES OF SOLIDS
2 (1)
2
(2) (3)
a
11 a 12
a 213 a12 a13 a13 a11 a11 a12
a2 a 222 a 223 a12 a23 a23 a21 a21 a 22 (2) (3)
21
a 231 a 232 a 233 a32 a33 a33 a31 a31 a 32
(4) (5) (6)
a21 a31 a22 a32 a23 a33 a22 a33 a21 a33 a21 a32 a23 a32 a23 a31 a22 a31
a a
31 11 a32 a12 a33 a13 a12 a33 a11 a33 a11 a32 a13 a32 a13 a31 a12 a31
a11 a21 a12 a22 a13 a23 a12 a23 a11 a23 a11 a22 a13 a22 a13 a21 a12 a21
(7) (8) (9)
(4) b (7) (6) (8) (5) (9) (9.31)
The variation in thermoelectric power with strain can also be established. For this purpose,
Eq. (9.27) is altered to give
ij mn
ij
kl ijmn smnkl kl (9.32)
mn
kl
or
in matrix subscript notation. Here Eik (ui /uEk ) is a polar fourthrank tensor called the elasto
thermoelectric power tensor and skj is the elastic compliance tensor given by Eq. (4.47). By comparing
Eqs. (9.28) and (9.33), the piezothermoelectric and elastothermoelectric power coefcients can be
related by reciprocity
ij Eikskj (9.34)
or its inverse
where ckj is the elastic stiffness modulus given by c s
1 as deduced from Eq. (6.36a) and thermody
namic symmetry discussed in Section 4.4.
The transformation law for the elastothermoelectric power tensor E is easily found from the
transformation laws for strain and thermoelectric power. Strain transforms as Ea A ~
1E or E A
~ Ea
(see Section 6.1.2) and transforms as a B. Because from Eq. (9.33) EsS EE relative to
coordinate axes 0xi and a EaEa relative to axes 0xia, it follows that
~ EaEaEa
a B BEE BEA
THERMOELECTRIC, PIEZOTHERMOELECTRIC, AND DIFFUSIVE EFFECTS 169
or
~
Ea BEA (9.36)
i ij s
i T T j T ik kj j , (9.37)
T T
T
giving the Thomson effect in terms of the piezothermoelectric and elastothermoelectric coef
cients. Here, it has been assumed that all thermal stresses are absent and that the tensor character
and aelotropism of and E are the same.
The anisotropy of the piezothermoelectric and elastothermoelectric coefcients and E is
determined by the standard methods emphasized in this text. Consider the array in Eq. (9.29),
which applies to the triclinic crystal system. The anisotropy of all crystal systems, other than the
trigonal and hexagonal, can be determined by the method of direct inspection as was done for the
piezoelectric moduli in Section 6.1.3. For the trigonal and hexagonal crystal systems, the brute
force method described in Section 6.1.4 must be used. Remember that the generalized quadratic
transformation form B must be used together with A in Eqs. (9.30) and (9.36) when applying the
bruteforce method. For the coefcient arrays of and E, see Tinder in Endnotes, Section VII.
piezothermoelectric effect. Here again, we assume that Rij is everywhere a continuous function of
temperature and stress and that its derivatives with respect to temperature T and stress Skl are real.
The resulting expansion is
n
1
ij (T , kl ) ( T T0 ) kl ij (T0 , 0 )
n 0 n! T kl
ij
ij
ij (T0 , 0 )
( T T 0
)
kl
T ( T0 , 0 ) kl ( T0 , 0 )
2
1
ij
2 ij
(T T0 ) 2
2 (T T0 ) kl
2! T 2 T
( T0 , 0 ) kl ( T0 , 0 )
2 j
i kl op L,
(9.38)
kl op ( T0 , 0 )
where Rij (T0, 0) and all tensor coefcients (in parentheses) are evaluated at temperature T0 and zero
stress. Notice that the secondorder effects, u2Rij / uTuSkl and u2Rij / uSkl uSop, represent the piezo
thermoresistive and quadratic piezoresistive effects, respectively. There will be no further discussion
of the secondorder effects, the remainder of which are selfexplanatory.
Assuming that all measurements are to be conducted at a reference temperature of T T0 and
that all second and higherorder terms in stress can be neglected, Eq. (9.38) becomes
ij
ij ij (T0 , kl ) ij (T0 , 0 )
kl ijkl kl ,
kl
( T0 , 0 ) (9.39)
where Pijkl is a fourthrank polar tensor called the piezoresistance tensor. Because both Rij and Skl are
symmetrical secondrank tensors, we can write
where it is understood that Pij x Pji . Thus, the piezoresistance tensor transforms the same as the
linear piezooptical coefcients given by Eq. (7.51) and is affected by crystal symmetry the same as
presented in Table 7.1.
THERMOELECTRIC, PIEZOTHERMOELECTRIC, AND DIFFUSIVE EFFECTS 171
13 c
J n L11
L
T T
Electrodiffusive effects
J m L31
L33 c
T T (9.41)
1 23 c
J q L22
L
T T
Thermodiffusive effects
m 1
J L32
L33 c
T T (9.42)
The reader has already been introduced to the phenomenological developments of the ther
moelectric effects in some detail including the application of Onsagers reciprocity principle as ap
plied to the phenomenological coefcients given in Eqs. (8.20). The interaction effects in Eqs.(8.20)
can be complex considering that charged matter (electrons, holes, ions) can carry charge, heat, and
mass at the same time and that different species can inuence other species. Although it is not our
intention to explore the electrodiffusive and thermodiffusive effects in detail, a short discussion of
the diffusive effects is necessary when dealing with the coupled effects in Eqs. (9.41) and (9.42).
s& Jim ,
i
(9.43)
i T
where Jim is the mass ux of the ith species and Mi is the chemical potential for the i th species. From
this we can generalize Ficks law in the modied form of Eq. (8.8) and under isothermal conditions
as the sum of diffusing species given by
m
Lij
Ji Nj Dij Nj ( x ). (9.44)
j T j
172 TENSOR PROPERTIES OF SOLIDS
Here, Nj (x) is the concentration (mole number) of the j th component at any position in Cartesian
space of the medium in which the diffusion is occurring. The problem now remains to relate the
phenomenological coefcient L ij with the physically measurable diffusion constant D ij . This re
quires the use of GibbsDuhem relation, Eq. (4.4) under constant temperature, electric, magnetic,
and stress elds together with the use of chemical thermodynamics as applied to the condensed
state.
For example, at constant T, E, B, and S, the GibbsDuhem relation for a nonindependent,
twospecies system and for arbitrary dx, is expressed as
where N1 is the mole number concentration of the (dilute) diffusing species and N2 N1 is the
mole number concentration of the host medium. Because diffusion ows do not produce a volume
change, it follows that
m m
J 1v1 J 2v2 0, (9.46)
where vi is the partial molar volume of the species i. Now, by introducing Eqs. (9.45) and (9.46) into
(9.43), the isothermal entropy density production for the twocomponent system becomes
r r r N r
1 N v
r 1
s& J1 1
J2 2
J1 1 J2 1 1 1 J1 (9.47)
T T N2 T N2 v 2 T
in vector notation. With the information in Eq. (9.47), Eqs. (9.44) and (9.45) combine to give the
linear force ux equation for the diffusing species as
r N v 1
J1 L11 1 1 1
D11 N1 . (9.48)
N2 v 2 T
But M1/N1 (uM1 / uN1), which allows
r 1 N v
For an ideal dilute condensed solution, the chemical potential for a single diffusing species is
M1 M0 RTln(X1), (9.51)
where M0 is the chemical potential in the reference state ( p, T ) independent of M1, R is the familiar
gas constant R 8.31 J/mol K, and X1 N1 / (N1 N2) N1 / N2 is the mole fraction noting that
N1 N2 for a dilute solution. Therefore, it follows that uM1 / uN1 RT / N1, giving the nal result
N1 D11 .
L11 = (9.52)
R
The addition of more diffusing species complicates the analyses signicantly because the dif
fusion cross (interference) effects must be taken into account. In this case, at least three diffusing
species are required to verify Onsagers reciprocal relations.
When dealing with electrodiffusive and thermodiffusive effects, it is clear that the diffusing
species can carry charge and heat. Clearly, the phenomenological developments of these systems
become excessively complex when multiple diffusing species are present in the system. The analysis
of a simple twospecies diffusion problem just discussed serves to illustrate this point.
175
C H A P T E R 10
Moving charges transport thermal energy as well as electrical charge and therefore interact with a
magnetic eld without regard to which quantity (heat or electric charge) is being transported. We
are interested in the various direct and cross (transverse) effects due to an electrochemical potential
m
gradient M
, a temperature gradient T, and a magnetic eld H . Although Chapter 9 dealt with
the thermoelectric effects in the absence of a magnetic eld, we now must consider these effects as
being a function of magnetic eld and alter Onsagers reciprocal relations accordingly.
n q 1 q 1
s Jxn x
Jy y
J x x
J y y
, (10.1)
T T T T
from which the phenomenological relations are found to be a truncated form of Eqs. (8.21) given by
(
J nx ( L11*) L12* ( L13*)
L14* x (
T
n 21*
( L24*) (
Jy
Jq
L
( L31*)
( L22*)
L32*
L23*
(L ) L
33* 34*
y T
.
(
qx
J y
L41*
x 1 T
( L42*) L43* ( L44*)
( )
1
y T
( ) (10.2)
176 TENSOR PROPERTIES OF SOLIDS
The coefcients (LAB*) in parentheses are related to the conductivities and are independent of mag
m
netic eld. This is because in the isotropic x,y plane with the magnetic eld vector H perpendicular
to that plane, the conductivity tensors are symmetrical and do not need to be divided into symmetri
cal and antisymmetrical parts. (Note that the thermoelectric power is also related to the conduc
m
tivities but is asymmetrical.) Therefore, the coefcients (LAB*) are called even functions of H , which
m m
means that LAB*(H ) LAB*(
H ) for A B or A x B. The remainder of the coefcients are related to
m
transverse effects (not related to the conductivities) and hence are odd functions of H , meaning that
m m
LAB*(H )
LAB*(
H ) for A x B. The asterisk (*) on the phenomenological coefcients allows a later
change to a new set of coefcients without the asterisk.
Now consider applying the consequences of an isotropic x, y plane to the coefcients of
m
even functions of H . For this, the following relations apply by isotropy in the x, y plane and by
Eqs. (10.2):
J nx J ny
or xx yy ( c 0 )
x ( / T )
y x T yT 0 y ( /T )
x x T yT 0
J qx J qy
and or kxx kyy
x (1 /T ) x y yT 0 y (1 /T ) x y x T 0
together with
J nx
J ny
( ) ( )
T
xx yy
x T x y y T 0 y x y x T 0 c 0
J qx J qy
(k / ) (k / )
and
, (10.3)
xx yy
x y xT y T 0 y
x xT y T 0 c 0
L11* L22*, L33* L44*, L24* L42*, and L13* L24* L31*. (10.4)
Then by applying the effect of Onsagers reciprocal relations (for twodimensional thermoelectric
m
ows) to the coefcients that are odd functions of H , we conclude that
L12*
L21*, L14*
L41*
L23* L32*, and L43*
L34*. (10.5)
EFFECT OF MAGNETIC FIELD ON THE TRANSPORT PROPERTIES 177
When these coefcient relationships are introduced into Eqs. (10.2), there results only six in
dependent phenomenological coefcients represented by the phenomenological relations given by
(
J nx
n
L11*
12*
L12* L13*
L14*
x (
T
(
Jy
Jq
L
L13*
L11*
L14*
L14*
L33*
L13*
L 34*
y (
T
qx
L14* L13* L34* L33*
T( )
x 1
J y
1
( )
y T
(10.6)
Mazur and Prigogine (see Endnotes) have shown that by partial inversion (using Legendre trans
forms) the algebra is greatly reduced when dening the various coefcients that have physical
meaning (e.g., the Hall coefcient).The idea here is to place the electrical uxes and temperature gra
dients, all of which are experimentally controllable, on the right side. When this is done, Eqs. (10.7)
sresult, which allows simple relationships to occur between the physically signicant coefcients. To
m M
accomplish this, we let J n m e J n, M
/e, and (1/T ) m T,such that the factors e, 1/e, and
1/T 2 are absorbed in the new phenomenological coefcients LAB with the asterisk (*) omitted. The
phenomenological relations now become
1
L11 L12 L13 L14
eJ nx
e x
1
L12 L11 L14 L13 eJ ny
TL13
e y .
TL14 L33 L34 x T
J qx
Jq TL14 TL13 L34 L33 y T (10.7)
y
The symmetry of the LAB coefcients in Eqs. (10.7) is implied by the LAB* in Eqs. (10.2), but
the LAB are fairly complicated functions of the LAB* coefcients. Note that the sign differences and
the appearance of the TLAB coefcients are a result of the partial inversion of Eqs. (10.2) and the
fact that the new coefcients have absorbed the factors e, 1/e, and
1/T 2.
We now dene the direct and transverse thermomagnetic and galvanomagnetic effects in a
homogeneous media (for which all Mc 0) as they apply to the homogeneous isotropic x, y plane
m
where the magnetic eld H is directed perpendicular to that plane. The four transverse effects are
the Hall effect, the Nernst effect, the Ettingshausen effect, and the LeducRighi effect, all depicted
in Figure 10.1. The two electron ux parameters J n, named as cause parameters, are produced by
the gradient M
eF, where
F is the common electrostatic potential gradient (electric eld
strength, E). Conversely, the two temperature gradients, named as cause parameters, each produce
178 TENSOR PROPERTIES OF SOLIDS
Transverse Transverse Transverse Transverse
H Gradient
H Gradient
H Gradient
H Gradient
y y T y T y
Jn T Jn T
Cause x Cause Cause x Cause
x x
Ettingshausen LeducRighi
Hall Effect Nernst Effect
Effect Effect
(a) (b) (c) (d)
FIGURE 10.1: The four transverse thermomagnetic and galvanomagnetic effects as they occur in the
x,y isotropic plane with the magnetic eld H applied normal to that plane.
a heat ux that is responsible for the transverse effect indicated. In dealing with the denitions of
these thermomagnetic effects that follow, this information must be kept in mind.
1 x 1 y
L13 L24 , (10.8)
e xT Jxn = J yn = yT = 0 e y T
Jxn J yn xT 0
which follows from the denition of y F / T, with Mc 0 in Eqs. (8.14) and (9.2).
2. Isothermal electrical conductivity
eJ nx eJ ny
I
(1 / e ) x
x y y
T T J n 0
(1 / e ) y xT = yT = J xn = 0
1 1
L11 L22
I
(10.9)
EFFECT OF MAGNETIC FIELD ON THE TRANSPORT PROPERTIES 179
eJ nx eJ ny
A
( 1 / e ) x xT J yn Jyq 0
(1 / e ) y yT J xn J xq 0
1
A L11 T ( L14 )2 / L33 (10.10)
J qx J qy
I
k
k I L33 L44 (10.11)
xT J xn J yn y T 0 y T J xn J yn xT 0
5. Adiabatic thermal conductivity
q
Jq Jy
k x
A
k A = L33 ( L33 ) 1 ( L34 ) 2 (10.12)
x T J xn J yn J yq 0 y T J xn J yn J xq 0
6. Isothermal Hall coefcient
1 y 1
RI
x
R I = L12 / H (10.13)
e n e n
He J x xT yT J y 0
n
He J y
xT y T J xn 0
7. Adiabatic Hall coefcient
1 y
1
x
RA
n n
e HeJ x J yq J yn xT 0 e HeJ y J xq = J xn = y T = 0
1 y 1 x
A
e H xT J xn =J yn =J yq = 0
e H yT J xn= J yn= J xq= 0
y T T
x n
TL14 / HL33 (10.17)
n
y T
T
x
L34 / HL33 (10.18)
H xT J xn = J yn = J yq= 0 H y
T J xn = J yn= J xq= 0
Notice that the transverse effects dened in Eqs. (10.13) to (10.18) are odd functions of the mag
netic eld strength H and require a sign reversal to accompany the coefcient denitions when the
x,y axes are reversed. This is a consequent of timeinversion operator discussed in Appendix A.
For the even functions of H (i.e., no function of H in these cases), there is no sign reversal accom
panying a reversal of axes.
With the denitions given in Eqs. (10.8) to (10.18) for the six isothermal coefcients, the
phenomenological relations in Eq. (10.7) can now be written as
1 x ( I ) 1 HR I
H I eJ nx
e n
1 e y HR I ( I )1 H I
eJ y
J q
T
TH I k I Hk I
xT
x
Jq TH I T
Hk I
k I y T (10.19)
y
There are certain relations inherent in Eqs. (10.19). These relations are as follows:
(S I) 1 (S A) 1 H 2 HIE, (10.22)
RA RI E, (10.23)
H I HA Z. (10.24)
That these expressions correctly express the simple relationships between direct and trans
verse effects is easily demonstrated. From the denition of the Ettingshausen coefcient, we can
derive Eq. (10.20) by using Eq. (10.17) with Eqs. (10.7) or Eqs. (10.19) as follows:
EFFECT OF MAGNETIC FIELD ON THE TRANSPORT PROPERTIES 181
yT
and y J ny 0.
HeJ nx Jyn = Jyq = xT = 0
Thus, Jyq 0 TL14eJxn L33yT or Jyq 0 TLH1eJxn k IyT. The result proves Eq. (10.20):
In a somewhat similar fashion, we can derive Eq. (10.24) from Eqs. (10.15) and (10.16) by
using Eqs. (10.7) and (10.19). We must rst nd HI and then HA:
I 1 y
.
e H xT J n J n T 0
x y y
1 y
A .
e H xT J n J n J q 0
x y y
From this, we have HA [L14
L13(L34 / L33)] / H . Now taking the difference between HI and HA
proves Eq. (8.102):
Proof of the remaining three expressions, (10.21)(10.23), will be left as exercises for the
reader.
and
By denition, RijS(H ) is an even function of the magnetic eld strength H, whereas RijA(H ) is an odd
function of H.
We now expand RijS(H ) in a Taylors series as an even function of the magnetic eld strength
H about the state of a reference temperature T 0 (not shown) and in the absence of heat and matter
currents. Thus, the expansion yields coefcients for n 0, 2, 4, ... in Eq. (2.52), with the result,
2 ij
iSj ( H ) ij ( 0 ) Hk Hl L
H H
k l
( 0 , 0 )
ij ( 0 ) ijkl Hk Hl L, (10.32)
where each term is evaluated at zero or near zero magnetic eld. Introducing Eq. (10.32) into
Eq. (10.28) gives
i ij ( 0 ) ijkl Hk Hl L J nj . (10.33)
The rst term on the right side of Eq. (10.33) gives the generalized Ohms law for which
Rij Rji in the absence of a magnetic eld. The second term in Eq. (10.33) represents the magne
toresistance effect. The fourthrank polar, nonmagnetic tensor Rijkl is called the magnetoresistance
tensor, which has partial symmetry in i, j m, and k, l n expressed as
Thus, Rmn transforms as Ra ARA
1, the same as Eq. (7.51), and is affected by crystal symmetry the
same as the piezooptical coefcients Pmn given in Table 7.1.
Expansion of RijA(H ) in a Taylor series as an odd function of the magnetic eld strength coef
cients for n 1, 3, ... in Eq. (2.52) gives
j
iAj ( H )
i H + H , (10.35)
H k ijk k
k (0)
where each term is evaluated at weak (nearzero) magnetic eld. Introducing Eq. (10.35) into
Eq. (10.28) gives the result
i ijk Hk L J nj .. (10.36)
The thirdrank tensor Rijk Rijk uRij / uHk is called the Hall tensor, and from Eq. (10.36), the Hall
eld is given by
Here, Eq. (10.37) agrees with the denitions in Eqs. (10.13) and (10.14) when we set M
eF
(chemical potential gradient is zero) and J n
J e / e as given in Section 8.5.
Because the magnetic eld H is an axial rstrank tensor, then the Hall tensor Rijk is a third
rank, axialmagnetic, antisymmetrical tensor (in indices i, k). However, any axial, antisymmetrical,
thirdrank tensor corresponds to a polar, secondrank tensor according to the single and double
contraction products given by Eqs. (2.65) and (2.69), respectively, and expressed here as
and
where it is understood that rkl x rlk. Thus, r transforms as in Eq. (2.13), and it is affected by crystal
symmetry the same as the thermoelectric power ij x ji components given in Table 9.1. Therefore,
the components of the Hall tensor Rijl can be obtained from the polar secondrank tensor rkl or vice
versa as provided in Eqs. (10.38) and (10.39) and by Table 9.1, assuming that data are available for
a given crystal system. Actually, magnetic eld strength H is an axialmagnetic vector that makes
Rijk an axialmagnetic, antisymmetrical tensor, and rkl a polarmagnetic tensor. But the designation
magnetic requires additional discussion, which is covered in Appendix A.
184 TENSOR PROPERTIES OF SOLIDS
Both Ohms law and the magnetoresistive effect contribute to Joule heating, but the Hall
effect does not. The Hall effect is by Figure 10.1(a), and Eqs. (10.13) and (10.14), a transverse
effectthe Hall eld is always perpendicular to the electric current and cannot contribute to any
Joule heat dissipation. Thus, any Joule heating is caused only by the symmetrical part of the resistiv
ity (or conductivity) tensor, as expressed in tensor form by Eq. (10.33) after multiplying both sides
by Jin.
and
r r r r r
J q k ( H e J n ) T e J n k ( H T ) k T . (10.41)
In Eq. (10.41), we have used the Bridgman relation kE T H given by Eq. (10.20). Notice that each
term in Eq. (10.40) represents an electrostatic potential and that each term in Eq. (10.41) represents
a heat ux density as, for example, in Eq. (9.11). Also, R and k are the electrical resistivity and ther
mal conductivity, respectively, and is the thermoelectric power coefcient, all taken as constants
in the isotropic solid. Note that, for selfconsistency, the terms in Eqs. (10.40) and (10.41) are taken
from the equations for
(1/e)y M
F Em and J q J q in Eq. (10.19). The resulting transverse
y
elds are consistent with Figure 10.1 and are dened as follows:
EFFECT OF MAGNETIC FIELD ON THE TRANSPORT PROPERTIES 185
m m
R(H s eJ n) y Hall electrostatic potential gradient (10.42)
m
H(H s T ) y Nernst electrostatic potential gradient (10.43)
m m
E(H s eJ n) y Ettingshausen temperature gradient (10.44)
m
Z(H s T ) y LeducRighi temperature gradient. (10.45)
Here, the coefcients R, H, E, and Z are all taken as constants for the isotropic solid. Implicit in these
denitions is the equality M
eJ in the absence of chemical potential gradients, M 0, and eJ n
c
e
J as given in Section 8.5. All thermomagnetic and galvanomagnetic eld gradients are assumed to
be positive in a direction corresponding to the righthand rule for the vector cross products. Thus,
these four transverse elds are always perpendicular to the causal vectors J n and T .
In tensor notation, the Hall, Nernst, Ettingshausen, and LeducRighi eld gradients must
be dealt with somewhat differently because they do not necessarily represent a transverse eld. To
begin with, these thermomagnetic and galvanomagnetic properties are all thirdrank tensors. The
Hall eld, previously given by Eq. (10.37), was obtained by expanding the electrical resistivity in a
power series. Similarly, we can obtain Nernst, Ettingshausen, and LeducRighi elds by expanding
the thermoelectric power, Peltier coefcient, and the thermal conductivity in their respective power
series. Or alternatively, we can deduce them from Eq. (10.19) and Figure 10.1. When this is done,
the results in tensor notation are given as follows:
iF N Hijk Hk jT (10.47)
iT L Zijk Hk jT . (10.49)
Here, each of the four thermomagnetic and galvanomagnetic properties are intrinsically related
to their respective asymmetrical, secondrank tensors via Eq. (2.69) but are also magnetic in na
ture. Thus, any axial, antisymmetrical thirdrank magnetic tensor property has intrinsic symmetry
equivalent to that of an asymmetrical, polar, secondrank magnetic tensor property. The subject of
186 TENSOR PROPERTIES OF SOLIDS
magnetic tensor properties and the subject of time reversal have purposely been left to Appendix A,
where they will be discussed in some detail.
Clearly, the number of higherorder magnetotransport effects greatly increases with property
tensor rank. This is easily understood when one considers that the three conductivities, for example,
can be expanded in power series as a functions of weak magnetic eld together with tempera
ture, electric eld, and stress. Add to these the thermomagnetic and galvanomagnetic effects also
expanded with these intensive elds and we have a very large number of very complex effects to
consider, many of which would involve property tensors of rank 7 and above. We will not continue
consideration of tensor properties higher than rank 6.
Much can be said about the partial intrinsic symmetry possessed by these higherorder mag
netotransport properties, and it is not difcult. For example, by expanding the thermoelectric power
in a Taylors series as a function of stress and magnetic eld, the secondorder (in H ) piezomagneto
thermoelectric power tensor would be represented as
3 ij
ijklmn . (10.50)
HkHl mn
Here, 'ijklmn is a partially symmetrical sixthrank tensor with symmetry in kl o and in mn p but
not in ij. Because ij , Smn , and the dyadic HkHl are all polar secondrank tensors, then 'ijklmn must
be a polar sixthrank tensor. Therefore, this piezomagnetothermoelectric power tensor can be rep
resented as 'ijopwith no further symmetry possible. Thus, it follows that
CharacteristicsofaKind
The reader will learn that to determine the character of a given tensor property, one needs to only
add up the characteristics of a kindan odd number of characteristicsofakind produces that
character, whereas an even number of characteristicsofakind does not. The major characteristics
ofa kind include axial, antisymmetrical, and magnetic. The polar tensor character is the norm
that can be overridden by any combination of the three characteristicsofakind. The inherent
symmetry designations, which include symmetrical, asymmetrical, and partial symmetrical, are also
needed to establish the transformation law for a given tensor. When all of the above have been
considered, there remains only the effect of crystal symmetry to completely identify the surviving
components of a given tensor property.
189
APPENDIX A
Up to this point, we have dealt with the 32 conventional point groups that are used to determine
the effect of crystal symmetry on polar tensor property components. Chapter 3 was devoted entirely
to this cause, and in subsequent chapters, only token mention was given to magnet tensor proper
ties and the magnetocrystalline classes that add new variants to those invoked by the conventional
crystal classes. Now it is necessary to delve further into the subject matter of this Appendix.
Condition 2. All materials are affected by magnetic elds to some degree or another. But
some materials are affected much more strongly by the presence of a magnetic eld than others and
may demonstrate a highly nonlinear B
H behavior. Some materials possess atomic spinmagnetic
moment alignments that are repeated periodically over the space lattice of the crystal and may
possess a remnant magnetism in the absence of a magnetic eld. Such materials (crystals) are clas
sied as magnetic materials. If the spinmagnetic dipole moment alignments in these materials are
altered by a magnetic eld, a purely spatial transformation, or both, then a special transformation
is needed to restore the materials dipole moments back to their original alignments. The charac
teristics just mentioned apply to the magnetic materials classied as ferromagnetic, ferrimagnetic,
or antiferromagnetic (dened in the Glossary). In contrast, there are the socalled nonmagnetic
materials, called paramagnetic and diamagnetic (also dened in the Glossary), that show little and
no signicant change, respectively, in their magnetic dipole moment alignments due either to the
presence of a magnetic eld or to spatial transformations. So, as a rule, for application of the 90
magnetocrystalline point groups, the material in which the magnetic tensor property is manifest
must be magnetic in nature and the domain alignment conguration must be known. Clearly, for
nonmagnetic crystals or for magnetic crystals at temperatures above the Curie (Nel) point, there
would be no need to apply the 90 magnetocrystalline point groups to a magnetic tensor property
because the conventional 32 point groups would sufce for symmetry purposes. Exceptions to this
rule appear in some paramagnetic subgroups. Therefore, assuming that conditions 1 and 2 are satis
ed, knowledge of the nature of the spinmagnetic domain structure will be necessary before the
magnetocrystalline point groups can be applied properly. Of course, if the spinmagnetic domain
structure is unknown or assumed (without experimental proof ) for a given magnetic tensor prop
erty, there is nothing preventing a complete analysis of the component arrays. However, carrying
out such an analysis may or may not be an exercise in futility.
where a is replaced by sas discussed in Section 3.5. For polar magnetic tensors,
1, and for
all other polar nonmagnetic tensors, 1 and is usually not included in polar tensor transformation
forms. Keep in mind that and ataken separately do not constitute a symmetry transformation.
But for axialmagnetic properties, their combination aa is complementary and must be
administered with great care. Also, it is customary to view ferromagnetic, ferrimagnetic, and some an
tiferromagnetic solids as magnetic for which either Eq. (A.1) or Eq. (A.2) must be applied to magnetic
tensor properties. Diamagnetic solids and most of the paramagnetic solids and their subgroups are
generally regarded as nonmagnetic for which Eqs. (A.3) and (A.4) apply. However, there are excep
tions to these rules. For further reading on this subject, see Endnotes, Section VI.
To illustrate, let us consider a few examples. The magnetic eld strength vector Hi is both
axial and magnetic, and its transformation law is represented as
In contrast, the magnetic susceptibility given in Eq. (4.46) is a principal effect and expressed as
Mi
ik 0 . (A.6)
Bk
Consequently, 9ik is a polar, symmetrical, secondrank tensor property because M and B are both
axialmagnetic in character. Thus, 9ik transforms as in Eqs. (2.13), (2.14), or (2.22).
Now consider the magnetoelectric susceptibility dened by Eqs. (4.57) and (4.58) and ex
pressed as
Mi
ij . (A.7)
Ej
The magnetoelectric susceptibility is an asymmetrical secondrank tensor that is both axial and
magnetic in character. Accordingly, if manifest in a magnetic material, it must transform as
where the latter two equations are given in matrix notation, with B representing the quadratic trans
formation matrix for asymmetrical secondrank tensors given by Eq. (9.31).
The Hall tensor Rijk given by Eq. (10.35) is an axialmagnetic thirdrank tensor property
expressed as
ij
Rijk , (A.9)
Hk
with the understanding that R is also antisymmetrical. The form of Eq. (A.10) is easily deduced as
~ ~
follows: RR H relative to the old axes 0xi and RaR aH a relative to the new axes 0xia. Disregard
ing operators a for the moment, H transforms as H aaH or Ha
1H aa^H a. Now, using
Eq. (2.22), we have the result
~ ~ ~
R H R a~ H RH ,
which yields Eq. (A.10) after the operators a are added. To avoid dealing with an antisym
metrical thirdrank tensor, we can use the permutation tensor as in Eq. (10.39) to produce the dual
of R given by
~
rkl = eijk Rijl or r = eR . (A.11)
r r. (A.12)
Now it is possible to use Eqs. (A.11) and the components found for rkla to determine those for Rijl.
magnetic tensor properties. There we learned that to apply Neumanns principle, we substituted s for
a and S for A in the transformation forms so as to make use of Tables 3.5 and 3.6. We also found it
useful to apply the method of direct inspection to all crystal classes (except for s(7) in the trigonal and
hexagonal classes) to reduce the calculation effort. Now, in dealing with the 90 magnetocrystalline
classes, we add another layer of complexity but normally only if conditions 1 and 2 are met. For axial
and polar tensor properties, we restate the Neumanns principles from Eq. (3.22) as follows:
This means that all 11 centrosymmetrical crystal classes will be lacking in oddrank polar ten
sor property components and evenrank axial tensor property components. These statements will
always be true, but the addition of the magnetic characteristicofakind adds new variants to the
crystal symmetry problem.
The reversal of the atomic spinmagnetic moments can be accomplished by the timeinversion
operator t
t. This reversal of spins by means of the operator (creating time inversion) is actu
ally a quantum mechanical quantity whereby spin reversal and current reversal correspond to time
inversion t m
t. To deal with this concept, crystallographers modify the conventional notation for
rotation, reection, and inversion given by n, m, and n
by adding the symbols n
, m
, and n
, respec
tively. Thus, underlining the symbol indicates the use of the timeinversion operator .
As an example, consider the pyromagnetic effect dened in Eq. (4.53) and expressed as
Mi ,
qi = (A.14)
T
where the pyromagnetic modulus qi is an axialmagnetic rstrank tensor (vector) that transforms as
q  a  aq or q  s  s q (A.15)
when the generating matrices given in Table 3.5 are used. Thus, all centrosymmetrical crystal classes
are potentially able to support pyromagnetic moduli according to Eq. (A.13). In general, we can say
that the pyromagnetic moduli will be absent in all classes for which \s \ sq
1. It is found that
31 of the 90 magnetocrystalline classes are potentially capable of exhibiting the pyromagnetic effect.
As an example, ferromagnetic cobalt (Co) has a hexagonal closepacked crystalline structure with
magnetic spin alignments parallel to the optic axis [0001]z. The magnetic point group required
for Co is 6/mm m, with generating matrices from Table A.1 given by s (4) m > x s (6) m > z
and s (14) z) given in Table A.2. From Table 3.5 and Eq. (A.15) for s(4) m > x with
1 and
\a \
, there results
194 TENSOR PROPERTIES OF SOLIDS
q1 1 0 0 q1 q1
q
 s  s q ( 1)( 1) 0 1 0 q q
2 2 2 ,
q3 0 0 1 q3 q3 (A.16)
which by Neumanns principle requires that q1 0. Now, applying s(6) m > z , Eq. (A.15)
becomes
q1 1 0 0 0 0
q
 s  s q ( 1)( 1) 0 1 0
q
q
.
2
2
2
q3
0 0 1
q3
q3
(A.17)
Equation (A.17) requires that q2 leaving only q3 as the surviving nonzero component for Co.
Application of the operator s(14) z does not change this result.
It is necessary to explain the results given in Eqs. (A.16) and (A.17). Application of s(4)
m > x changes both the handedness of the coordinate axes and the spinmagnetic moment
alignments for which, in this case, the two operators are independent. Hence, \s \
1
1
1. Application of s(6) m > x also changes both handedness of the coordinate axes and the
spinmagnetic moment alignments, but now \a \
1 is a sufcient symmetry operation to
restore complete spacetime congruency to the crystal structure. Hence, \s \1
1
1.
It must be remembered that and \s \ are complimentary operators allowing \s \ to act on behalf
of both space and time transformations for some generating matrices. Thus, the reader is ad
monished to exercise great care in the use of Eq. (A.2), the most common transformation form
for magnetic properties. For example, in ferromagnetic and ferrimagnetic crystals, it is neces
sary to know the orientation of the spinmagnetic domain alignments so as to properly apply
Eq. (A.2).
As a second example, consider the magnetoelectric susceptibility tensor dened by Eq. (A.7),
which is an asymmetrical, axialmagnetic, secondrank tensor property. To begin with, its property
coefcients will be absent in all conventional centrosymmetrical groups. The effect can exist in
groups with both space and time inversion and in some noncentrosymmetrical groups. For example,
_
the magnetic point group _ 3 m applies to the ferromagnetoelectric crystal Cr2O3 below the Curie
_
(Nel) point. From Table A.1, _3 m has generating matrices s(4) m > x and s(13) 3_z given in Table
A.2. Applying m > x rst to Eq. (A.8) gives the result
MAGNETIC TENSOR PROPERTIES AND SPACETIME TRANSFORMATIONS 195
1 0 0
11 12 13
1 0 0
 s  s ~
s ( 1)( 1) 0 1
0 21 22 23
0 1
0
0 0 1 31 32 33 0 0 1
11 12 13
21 22 23
31 32 33 (A.18)
Therefore, L12L13L21L31 by Neumanns principle. Next, applying (3_ z);s(1)s(7)= yields
1 2 3 2 0 11 0 0 1 2 3
2
0
~ 3
 s  s s ( 1)( 1) 2 1 0
0 22 23 2 3 1 0
2
2
0 0 1
0 32 33
0 0 1
( 1 4 11 3 4 22 )
3
( 3 4 11 3 4 22 ) 3
2
(
23 )
( 4 11 3 4 22 ) ( 3 4 11 1 4 22 ) ( 1 2 23 )
33
(3
2
32 ) ( 1 2 32 ) (A.19)
11 0 0
= 0 22 23 .
0 32 33 (A.20)
But by Neumanns principle, the equality of Eqs. (A.19) and (A.20) can be justied only if L11 L22
_
and L23 L32 0. Therefore, the magnetoelectric susceptibility array for point group 3_ m must be
11 0 0 1 0 0
( 3 m )
0 11 0
0 1 0
.
0 0 33 0 0 3
(A.21)
INTERNATIONAL MINIMUM
CRYSTAL SYMBOL (SHORT GENERATING
SYSTEM FORM) MATRICES
_
Triclinic 1_ s(1)
Monoclinic 2 s(2)
m s(5)
2_ / m s(2), s(5)
2 / m
_ s(2), s(5)
2_ / m
_ s(2), s(5)
Tetragonal 4 s(9)
4_ s(11)
42 2 s(12), s(9)
MAGNETIC TENSOR PROPERTIES AND SPACETIME TRANSFORMATIONS 197
INTERNATIONAL MINIMUM
CRYSTAL SYMBOL (SHORT GENERATING
SYSTEM FORM) MATRICES
4m m s(4), s(9)
4_ 2m s(12), s(11)
4_ 2m s(12), s(11)
42m s(12), s(11)
Trigonal ++ s(13)
32 s(12), s(7)
3m s(4), s(7)
3_ / m
_ s(4), s(13)
_
3_ m s(4), s(13)
_
3_ m_ s(4), s(13)
Hexagonal 6 s(14)
6_ s(15)
6 / m
_ s(6), s(14)
6_ / m s(6), s(14)
6_ / m
_ s(6), s(14)
198 TENSOR PROPERTIES OF SOLIDS
Cubic m
_ 3 s(4), s(10)
432 s(8), s(10)
4_ 3m s(16), s(10)
m3m s(4), s(10), s(17)
m3m s(4), s(10), s(17)
m3m s(4), s(10), s(17)
TABLE A.2: Combinations s(11)  s(17) of the 10 basic generating matrix operators used in
Table A.1 and in Table 3.6
( 6 z) s
(1 )
s
(14 )
s
(15 )
, ( 4 x) = s
(1 )
s
(8 )
=s
(16 )
, m (110 ) = s
(4)
s
(9)
=s
(17)
,
MAGNETIC TENSOR PROPERTIES AND SPACETIME TRANSFORMATIONS 199
used in connection with those for the 32 conventional point groups given in Table 3.6. Together,
these two sets of point groups make up a total of 90 point groups that are commonly referred
to as magnetic point groups. Strictly speaking, of course, only the 58 point groups involve time
inversion.
Proper use of Table A.1 requires some explanation. Time inversion is represented by the
symbols n, m, and n
_ , denoting rotation, reection, and inversion, respectively. Combinations of
the 10 basic generating operators used in Table A.1 are given in Table A.2. The rule to follow is that
the timespace operators \s \ must be applied to the appropriate transformation form and then
only with use of the generation matrix required by the point group. Given change in the handedness
of the coordinate axes for a given generation matrix operation (\s \1,) the tricky part is to know
how to apply the timeinversion operator . The examples in Eqs. (A.16) and (A.17) are typical. In
Eq. (A.16), the operation s(4) m > x changes both the handedness and magnetic domain align
ments, but independently, requiring that \a \
1
1 . However, application of s(6) m > z
again changes both, but dependently, thereby requiring \a \1
1 .
To apply the combinations in Table A.2 to the magnetic point groups in Table A.1, it is nec
essary to know how to use time inversion. The rule is straightforward. Time inversion for operator
combinations must be applied to the resultant matrix operator. Typical examples are s(13) = s_(1) s(7)
(3_ z), s(14) s(3)s(7) (6z), and s(15) s(1)s(14) (6_z). Thus, the matrix multiplication indicated must be
carried out before applying time inversion. Other examples that are not combinations include s(2)
(2y), s(7) (3z), and s(8) (4x). The reader should refer to Tables 3.5 and 3.6 as needed.
Remember that the symbols n, m, and n
_ require the use of the timeinversion operator
which is used only to establish congruency of the spinmagnetic domain alignments after a trans
formation of axes. However, because the operator combination \s \ is complementary, care must
be taken to know whether the congruency of the alignments is established by \s \, as in the case of
Eq. (A.17). Thus, if a given group transformation changes the handedness of the coordinate axes for
an axialmagnetic crystal, it is necessary to know what effect the axial operator \s \
1 has on the
spinmagnetic domain alignments. Only then can the timeinversion operator be applied appro
priately. This, of course, is the reason why it is necessary to know the magnetic domain structure be
fore any symmetry group transformation. If, as for the nonmagnetic materials, the magnetic domain
structure is of no consequence, then 1 and only \s \ must be considered for an axialmagnetic
tensor property.
For further reading regarding subject matter presented in Sections A.3 and A.4, see
Newnham, Billings, and Birss in Endnotes, Section VI. The examples given in Section A.3 follow
closely those presented by Newnham.
201
Endnotes
An exhaustive bibliography for the subjects covered in this text would be enormous and would not
serve the reader well. Consequently, we carefully select those references that provide support for
material covered in this text and further reading for those needing additional information. It will be
noticed that many of the references that follow date back 40 years or older. This is expected because
it was in that era that most of the important fundamental work was established in tensor properties
of solids. It is for this reason that these references are frequently cited by current authors.
S. Bhagavantam, Crystal Symmetry and Physical Properties, Academic Press, New York, 1966.
H. B. Callen, ThermodynamicsAn Introduction to the Physical Theories of Equilibrium Thermostatics
and Irreversible Thermodynamics, John Wiley & Sons, New York, 1960.
W. P. Masson, Crystal Physics of Interaction Processes, Academic Press, New York, 1966.
I. Prigogine, Introduction to Thermodynamics of Irreversible Processes, John Wiley & Sons, New York,
1967.
S. R. De Groot, Thermodynamics of Irreversible Processes, NorthHolland, Amsterdam, 1963.
S. R. De Groot and P. Mazur, NonEquilibrium Thermodynamics, NorthHolland, Amsterdam, 1962.
D. Kondepudi and I. Prigogine, Modern Thermodynamics, John Wiley & Sons, New York, 1998.
L. D. Landau and E. M. Lifshitz, Electrodynamics of Continuous Media, Pergamon Press, Oxford, 1960.
A. C. Smith, J. F. Janak, and R. B. Adler, Electronic Conduction in Solids, McGrawHill, New York,
1967.
ENDNOTES 203
W. L. Bond, The mathematics of the physical properties of crystals, Bell Systems Tech. J. 22, 172,
1943.
E. Prince, Mathematical Techniques in Crystallography and Material Science, SpringerVerlag, Berlin,
1994.
D. E. Bourne and P. C. Kendall, Vector Analysis and Cartesian Tensors, 3rd ed., Chapman & Hall,
London, 1992.
E. C. Young, Vector and Tensor Analysis, Marcel Dekker, New York, 1993.
R. E. Newnham, Properties of Materials, Anisotropy, Symmetry, Structure, Oxford University Press, 2005.
A. R. Billings, Tensor Properties of MaterialsGeneralized Compliance and Conductivity, Wiley
Interscience, John Wiley & Sons Ltd., New York, 1969.
204 TENSOR PROPERTIES OF SOLIDS
P. Mazur and I. Prigogine, Galvanomagnetic and Thermomagnetic Effects, J. Phys. Radium 12,
616, 1951.
R. F. Tinder, Piezothermoelectric effects in anisotropic media, J. Appl. Phys., 43(6), 25222529,
June 1972.
Richard C. Dorf, editor in chief, The Electrical Engineering Handbook, 2nd ed., CRC Press and
IEEE Press, Boca Raton, FL, 1997.
R. E. Newnham, Properties of Materials, Anisotropy, Symmetry, Structure, Oxford University Press,
Oxford, 2005.
Standards on piezoelectric crystals, Proc. IRE. 37, 13781385, 1949.
W. L. Bond, Crystal Technology, John Wiley & Sons, New York, 1976.
205
Cause parameter. Usually, an intensive parameter that, when related to an extensive (effect) pa
rameter, defines a tensor property.
CCW. Counterclockwise (positive rotation).
Center of symmetry. A fundamental macroscopic operation involving an inversion of Cartesian
axes through the origin of coordinates.
Centrosymmetrical crystal class. A point group that contains a center of symmetry.
Characteristicsofakind. As used in this book, tensor characteristics that include axial, mag
netic, and antisymmetrical designations that can override the normal (polar) character of a tensor.
Chemical potential gradient. The chemical driving force responsible for the diffusion of
chemical species in a given medium as, for example, in the application of a concentration gradi
ent in Ficks law.
Clamped condition. A measurement condition that requires a given extensive parameter to re
main constant.
Closed system. As used in this text, a system that can only exchange energy with its surroundings
but not mass or charged mass.
Cofactor. The determinant minor of a square matrix obtained by crossing out the ith row and jth
column and multiplied by (
1)(i+j).
Compliance matrix. A property matrix generated from the equations of state for which the exten
sive parameters are given as functions of the intensive parametersthe inverse of the rigidity matrix.
Concentration gradient. In most cases, the same as the chemical potential gradient.
Conformable matrices. If A is an m sn (rows s columns) matrix and B is an n s p (rows s columns)
matrix, then A and B are conformable in the order AB. Hence, the number of columns in A must be
equal to the number of rows in B.
Conjugate parameters. Parameters that are intrinsically (physically) related as, for example, stress
and strain, temperature and entropy, and electric current flux and electrostatic potential gradient.
Conventional point group. One of 32 point groups into which all seven possible crystal systems
can be classified as to their macroscopic symmetry elements.
Convergence of a tensor. The single contraction product of a field tensor with the vector opera
tor that gives at each point on an element the net rate per unit volume at which a physical entity is
incoming to that element (opposite of the divergence of a tensor).
Converse effect. An independent coupled effect derived from a Maxwell relation for the direct/
converse effects expressing the rate of change of an extensive parameter with an intensive parameter.
Converse piezoelectric effect. The polar thirdrank tensor property expressing the change in
elastic strain as a function of the applied electric field.
CottonMouton effect. The polar, nonmagnetic, fourthrank tensor property representing the
quadratic magnetooptical effect that is produced when a dielectric is placed in a magnetic field such
GLOSSARY OF TERMS AND EXPRESSIONS 207
as to produce a phase difference or retardation between the linearly polarized light wave in the di
rection of the magnetic field and a wave propagating in a plane perpendicular to the magnetic field.
Coupled effect. An interaction effect not relating conjugate parameters but which constitutes
a Maxwell relation derived from a suitable thermodynamic potential such as the Gibbs free en
ergy density.
Crystallographic direction. The direction in a crystalline lattice designated by Miller or
MillerBravais indices that are determined by the lattice vector magnitudes along the crystal
lographic axes.
Crystallographic plane. The set of Miller or MillerBravais indices derived from the reciprocal
of intercepts on the crystallographic axes that define a plane.
Crystal system. One of seven sets of unit cell axes and angles into which all crystals must belong.
Curie point. A secondorder phase transition at a temperature for the ferromagnetic
paramagnetic change.
Current density. A flux representing the flow of charge, heat, or mass crossing a unit area per
second.
Dependent coupled effect. An effect relating any two intensive parameters with the correspond
ing two extensive parameters that derive from the appropriate choice of thermodynamic potential
together with the application of Greens theorem in a plane.
Dependent variable. The variable taken as the function of an independent variable in defining a
given property.
Diad. In crystallography, a twofold (180o) rotation axis of symmetry.
Diamagnetic solid. A solid whose magnetic susceptibility is negative and that exhibits a zero net
magnetic moment in the absence of an externally applied magnetic field but that produces a small
net magnetic moment that opposes an applied magnetic field.
Diathermal system. Any system that permits the flow of heat with the surroundingsa perfect
heat conductor.
Dielectric constant. The secondrank, polar tensor property equal to the relative permittivity
tensor.
Dielectric impermeability. As used in this text, the symmetrical secondrank polar tensor whose
components are used to phenomenologically develop the optical properties of crystals.
Dielectric susceptibility. The rate of change of polarization with electric field all multiplied by
the reciprocal of the permittivity in a vacuum.
Diffusion. The movement of a matter species under the influence of a chemical potential (con
centration) gradient.
Diffusivity. The secondrank tensor transport property relating the flux of matter to a chemical
potential gradient.
208 TENSOR PROPERTIES OF SOLIDS
Direct effect. An independent coupled effect derived from a Maxwell relation for the di
rect/converse effects expressing the rate of change of an extensive parameter with an intensive
parameter.
Direct inspection method. A simple deductive means of applying Neumanns principle by using
the minimum generating matrices applied to the crystal classes other than those containing a three
or sixfold rotation axis of symmetry.
Divergence of a tensor. The single contraction product of a field tensor with the vector operator
that gives at each point on an element the net rate per unit volume at which a physical entity is is
suing from that element. (opposite of the convergence of a tensor).
Double refraction. A beam of light traversing an anisotropic medium, such that the beam is sep
arated into two components, distinguished as the ordinary and extraordinary rays, that are polarized
at right angles to each other, that have different velocities within the medium, and that propagate
in different directions (same as birefringence).
Driving force. An affinity (potential gradient) that produces an irreversible process.
Dual of a tensor. A tensor or rank (r + 1) resulting from the application of alternating (permuta
tion) tensor on another tensor of rank r.
Dummy suffix. A repeating subscript.
Dyadic product. As used in this text, an outer product involving two firstorder tensors (vectors)
to form a secondrank tensor combination having nine components.
Effect parameter. Usually, an extensive parameter which when related to an intensive (cause)
parameter defines a tensor property.
Einstein summation convention. The implied summation(s) over the dummy (repeating)
suffix(s) or subscript(s) in a tensor equation.
Elastic strain. The extensive parameter that when related to a stress parameter defines an elastic
compliance coefficient or elastic stiffness coefficient as in Hookes law or its inverse.
Elasticity. The reversible process whereby the application of a stress to a solid produces a defor
mation (elastic strain) that is completely recoverable upon removal of the causal stress.
Elasto. A prefix denoting the influence of elastic strain on a physical property.
Elastooptical effect. The fourthrank, partially symmetrical, polar tensor property that express
es the rate of change of the impermeability tensor with the strain tensor and that is also related to
the piezooptical effect via the elastic stiffness or elastic compliance moduli.
Elastothermoelectric power effect. The partially symmetrical fourthrank, polar tensor property
that expresses the rate of change of the thermoelectric power with strain.
Electric dipole moment. A vector formed by the combination of two equal but opposite charge
distributions multiplied by the distance that separates the combination and directed from the nega
tive to the positive charge distribution.
GLOSSARY OF TERMS AND EXPRESSIONS 209
Electric field. The negative of the electrostatic potential gradient produced between opposite
charge distributions that are separated by finite distance. A measure of the torque on a unit electric
dipole.
Electrical conductivity. The secondrank, polar tensor property that relates an electric current
density to an electrostatic potential gradient (electric field).
Electrical resistivity. The secondrank, polar tensor transport property (inverse of the electrical
conductivity) that relates an electrostatic potential gradient (electric field) to an electric current
densitygeneralized Ohms law.
Electro. A prefix denoting the influence of electric field strength on a physical property.
Electrocaloric effect. The polar vector property that gives the change in entropy with electric
field strength and whose coefficients are the same as those for its corresponding pyroelectric effect.
Electrochemical potential. The total energy per particle equal to the sum of the chemical po
tential per particle and the electrostatic potential per particle. Also called the Fermi level in the
equilibrium state.
Electrodiffusive effect. Any effect that results from the simultaneous flow of electricity and mass.
Electrostatic potential gradient. Minus the electric field strength produced between opposite
charge distributions separated by finite distance.
Electrostriction. The elastic strain produced in a crystalline solid by the application of an electric
field. The converse piezoelectric effect.
Energy density. The energy per unit volume as, for example, internal energy density.
Enthalpy. The Legendre transform of the Euler relation that replaces all extensive parameters
(except entropy) by their conjugate intensive parameters as the independent variables and is the
thermodynamic potential used to define the heat capacity of a solid at constant electric field, mag
netic field, and stress.
Entropy. The negative change of Gibbs free energy with temperature at constant electric field,
magnetic field, and stress.
Entropy production. The time variation of unrecoverable work per unit volume per unit tem
perature inside a closed system and which must be positive definite if an irreversible process is
to occur.
Equation of state. A characteristic equation in thermodynamics, empirical or derived, expressing
the functional relationship between an extensive parameter and all relevant intensive parameters
and vice versa for an intensive parameter.
Equilibrium thermodynamics (thermostatics). The field of study for which all systems are re
quired to be in thermodynamic equilibrium.
Ettingshausen effect. The generation of a transverse temperature gradient when a magnetic field
is imposed in a direction perpendicular to an electric current flux.
210 TENSOR PROPERTIES OF SOLIDS
Euler relation. A thermodynamic potential that combines the first and second laws of thermo
dynamics in terms of the product of conjugate parameters and is used in the creation of the 16
thermodynamic potentials from Legendre transforms.
Even function. A function that does not change sign when the dependent variable changes sign
as in f (x) = f (x) (see odd function).
Exact differential. A differential that is path independent as, for example, the infinitesimal
change in internal energy in the first law of thermodynamics.
Extensive parameter. Extensive parameters are those that depend on the amount of material of a
solid phase system, hence volume or size dependent.
False effect. A false or secondary effect, usually of higher tensor order than the true (primary)
effect, occurs by indirect means, and functions as a correction factor to the primary effect.
Faraday effect. When a transparent isotropic crystal is placed in a strong DC magnetic field and
linear polarized light travels parallel or antiparallel to the magnetic field, the plane of polarized light
is rotated through an angle.
Faraday rotation. The angle through which the plane of polarized light is rotated as a result of
the action of the Faraday effect.
Faraday tensor. A polar nonmagnetic secondrank tensor that is related to the Faraday rotation
angle.
Fermi energy. As used in this text, the same as the electrochemical potential of electrons assum
ing equilibrium conditions.
Ferrimagnetic solid. A solid that has spontaneous antiparallel alignment of the magnetic dipole
moments but with incomplete cancellation, that shows hysteresis, and whose magnetism disappears
at the Curie temperature.
Ferromagnetic solid. A solid that has spontaneous aligned atomic magnetic dipole moments
(a remnant magnetization) in the absence of a magnetic field, that shows hysteresis, and whose
spontaneous magnetism disappears at the Curie temperature.
Ficks law. An irreversible transport process in which the diffusing matter flux is proportional to
a corresponding chemical potential (concentration) gradient.
Flux. The flow of electric current, heat, or mass across a unit area per second in a transport
process.
Force. In an irreversible system, the driving force is a potential gradient responsible for producing
a flux. In an equilibrium system, the force applied to a unit area of a solid defines a stress.
Fouriers law. An irreversible transfer process in which the diffusing heat flux is proportional to
the temperature gradient.
Free condition. A measurement condition that requires a given intensive parameter to
remain constant.
GLOSSARY OF TERMS AND EXPRESSIONS 211
Galvanomagnetic effect. One of several effects that results from the application of an electrostatic
potential gradient perpendicular to a magnetic field and producing either a transverse electrochemi
cal potential gradient or a transverse temperature gradient. Examples are the Hall, magnetoresis
tance, and Ettingshausen effects.
Generating matrix. One of 10 symmetry operations used in the generation of the 32 point groups.
Generation operator. A minimum generating matrix used to determine the effect of crystal sym
metry on the components of a property tensor.
GibbsDuhem equation. An expression showing that small increments in the intensive variables
cannot all be independent.
Gibbs free energy. A Legendre transform of the Euler relation that replaces all extensive param
eters by their conjugate intensive parameters as the independent variables.
Gradient of a scalar. See scalar gradient.
Gradient of a tensor. The outer product of a field tensor of rank r with a tensor operator of rank
n resulting in a tensor of rank r + n.
Grneisen tensor. In its general form, the Grneisen tensor expresses the rate of change in stress
with internal energy density and is proportional to the inverse of the isometric piezocaloric coefficient.
Hall effect. The generation of a transverse electrochemical potential gradient when a magnetic
field is imposed in a direction perpendicular to an electric current flux.
Heat capacity. As used in this text, a scalar expressing the rate of change of entropy density with abso
lute temperature (at constant electric, magnetic, and stress fields), multiplied by the absolute temperature.
Helmholtz free energy. The Legendre transform of the Euler relation that replaces the entropy
by temperature as the independent variable.
HermannMauguin International Short System. The system of symbols used in this text to
represent the symmetry elements characteristic of each of the 32 conventional crystal classes or
point groups.
Hermitian tensor. As used in this text, a secondrank tensor property for which the optical ab
sorption factor is zero.
Hexad. In crystallography, a sixfold (60o) rotation axis of symmetry.
Holohedral group. A point group that contains a center of symmetry. Same as a centrosym
metrical group.
Hookes law. The proportionality of stress to strain as a suitable description of the behavior of
solids in the elastic range.
Identity matrix. A square matrix for which the leading diagonal components are +1, all others
being zero.
Independence of path principle. A principle given to a thermodynamic property whose changes
depend only on its initial and final states as expressed mathematically by Greens theorem in a plane.
212 TENSOR PROPERTIES OF SOLIDS
Independent variable. The variable whose change causes a corresponding change in the depen
dent variable via the system property that links the two variables.
Index of refraction. A measurable quantity equal to the ratio of the velocity of light in a vacuum
to that in a given material; also, equal to the square root of the dielectric constant (relative permit
tivity) of a medium.
Indicatrix. An ellipsoid, whose major and minor axes are the principle axes of the dielectric con
stant tensor, which is descriptive of the passage of light through a crystal and must satisfy the
symmetry of the crystal. A plane cutting the indicatrix ellipsoid and passing through its center
will intersect the surface generally as an ellipse having a normal along the direction of light propa
gation. The light resolves into two components with wave fronts that lie along the semiaxes of the
ellipse and having refractive indices that are proportional to the lengths of the semiaxesthe major
axis represents the slower component, whereas the minor axis represents the faster component.
Inexact differential. Inexact differentials are pathdependent differentials called Pfaffians.
Inner product. The single contraction product of two tensors A B, which results in a tensor of
rank 2 less than the sum of the ranks of the two product tensors, that is rA + rB 2.
Intensive parameter. An intensive parameter is independent of the volume or size of a given
system such that if subsystems are adjoined, the intensive parameter of the whole is the same as
those of its parts.
Interaction diagram. As used in this text, a diagram consisting of intensive and extensive pa
rameters representing the firstorder properties given by the principle, coupled, and dependent
coupled effects.
Interaction effect. See coupled effect.
Inverse of a matrix. The inverse (reciprocal) of a matrix M is the transpose of the cofactor of each
element of M divided by the determinant of M.
Irreversible process. Any nonreversible process for which the entropy production is positive
definite.
Irreversible thermodynamics. The thermodynamics of transport (irreversible or Markoff )
processes.
Isentropic process. Any thermodynamic process in which the entropy is maintained constant at
each step in the process, hence also an adiabatic process that is reversible.
Iso. A prefix denoting constancy or uniformity of a field tensor.
Isolated system. A system that does not exchange energy, mass, or charged mass with its
surroundings.
Isometric. As used in this text, constant strain.
Isopiestic. As used in this text, constant stress.
Isothermal condition. Constant temperature condition.
GLOSSARY OF TERMS AND EXPRESSIONS 213
Isotropic solid. Any solid in which a property is invariant with direction in the solid.
Joule heat. The heat generated by the passage of electric current in a conductor.
Kelvin relation. One of two relations used in the expression of the thermoelectric effects and that
exist as a consequent of Onsagers reciprocal principle.
Kerr effect. A quadratic electrooptical effect that occurs when an isotropic solid becomes aniso
tropic in the presence of a magnetic field.
Kronecker delta. In Cartesian tensor analysis, the function Dij takes the value Dij = 1 if i = j or the
value Dij = 0 if i xj and forms a unitary matrix.
Lattice parameter. A length representing the size of the unit cell in a crystalline lattice.
LeducRighi effect. The generation of a transverse temperature gradient when a magnetic field
is imposed in a direction perpendicular to a heat flux.
Legendre transform. A transform that simultaneously replaces as the independent variable one
or more of the extensive parameters by their conjugate intensive parameters.
Maclaurin series expansion. A special case of a Taylors series expansion such that the expansion
is taken about the state of zero reference values for all variables involved in the expansion.
Magnetic dipole moment. Per unit volume, the magnetic dipole moment is the magnetization.
Magnetic field strength. A derived axial magnetic vector H that is associated with the external
magnetic flux density B and that is independent of the magnetic properties of the material in which
it is manifest.
Magnetic flux density (magnetic induction). The observable (external) axial magnetic vector
B associated with a magnetic field strength and equal to that magnetic field strength H times the
permeability of the substance in which H is present.
Magnetic point group. One of 90 selfconsistent magnetic symmetry operations (point groups)
that introduce the timereversal operator whose application together with the symmetry elements
of a conventional point group bring the spatial and magnetic moment orientations of a crystal into
selfcongruence.
Magnetic solid. As used in this text, any crystalline solid that is ferromagnetic, ferromagnetic,
or antiferromagnetic in nature and that possesses both conventional crystallographic symmetry and
timereversal symmetry elements.
Magnetic susceptibility. A secondrank tensor property that expresses the rate of change of mag
netization with magnetic field strength.
Magnetic tensor. A tensor whose components transform as a polar tensor but that may also be
affected by the timereversal operator for certain crystals.
Magnetization. The magnetization (relative permeability) is the negative change in the Gibbs
free energy density with magnetic flux density and is equal to the magnetic susceptibility per unit
magnetic field strength applied. The total magnetic dipole moment per unit volume of solid.
214 TENSOR PROPERTIES OF SOLIDS
Magneto. A prefix denoting the influence of the magnetic field strength on a physical property.
Magnetocaloric effect. A firstorder axial magnetic tensor property that produces a change in
the entropy density of a crystal with magnetic flux density and whose components are the same as
those of the pyromagnetic effect.
Magnetoelectric susceptibility effect. The independent coupled effect that expresses the rate of
change of polarization with magnetic flux density or its converse effect expressing the rate of change
of magnetization with electric field strength.
Magnetooptical effect. Any one of several linear or quadratic effects where the dielectric imper
meability tensor is caused to change as a result of a changing magnetic flux density vector together
with possible changes in temperature, electric field, and stress.
Magnetoresistance effect. The fourthrank tensor property that expresses the effect of second
order magnetic field strength on the electrical resistivity.
Magnetothermoelectric power effect. The fourthrank tensor property that expresses the effect
of secondorder magnetic field strength on the Seebeck or Peltier tensors.
Markoff process. As used in this text, transport processes for which the fluxes at any given in
stant depend only on the forces (affinities) in effect at that instanta transport process that has no
memory.
Matrix. A rectangular array of scalars or matrix elements that conforms to certain rules of com
bination with other matrices but whose elements can represent physically meaningful coefficients
or moduli.
Matter tensor property. As used in this text, any tensor effect or property associated with
a solid.
Maxwell relations. As distinguished from Maxwell equations in electromagnetic theory, Maxwell
relations are used to equate the coefficients of the offdiagonal coupled effects as allowed by ther
modynamic symmetry.
Method of direct inspection. A simple deductive means of applying Neumanns principle by us
ing the minimum generating matrices applied to the crystal classes other than those containing a
threefold or sixfold rotation axis of symmetry.
Microscopic reversibility, principle of. As used in this text, it states: For a system in the thermo
dynamic equilibrium, every type of micromotion occurs just as often as its reverse.
Miller indices. A notation used to describe crystallographic planes and directions for the six
crystal systems.
MillerBravais indices. A alternative notation used to describe crystallographic planes and direc
tions for the trigonal and hexagonal crystal systems.
Mirror plane. A plane of reflection that is equivalent to a center of symmetry followed by a 180o
rotation about the mirror plane normal.
GLOSSARY OF TERMS AND EXPRESSIONS 215
Particle. As used in this text, a positive test charge equal to the absolute value of the charge on
an electron.
Peltier effect. The evolution or absorption of heat accompanying the flow of electric current
across and isothermal junction between two dissimilar conductors or semiconductors.
Permeability. A polar secondrank property tensor that is the ratio of the magnetic flux density
vector to the magnetic field strength vector.
Permittivity. A polar secondrank property tensor that is proportional to the dielectric constant
tensor.
Permutation tensor. An axial, antisymmetrical tensor of rank 3 that takes the value of +1 for an
even permutation of 123, the value of
1 for an odd permutation of 123 (e.g., 132), and is zero if
any two of the subscripts are the samealso called the alternating tensor.
_
Pfaffian. An inexact differential that is path dependent as, for example, the external work d W
done on a solid phase systemthe external work depends on the path taken between initial and
_
final states when integrating d W.
Phenomenological development. As used in this text, property developments based mainly on
equilibrium and irreversible thermodynamics arguments.
Piezo. A prefix denoting the influence of mechanical stress on a physical property.
Piezocaloric effect. A secondrank polar tensor property expressing the rate of change of entropy
density with stress whose coefficients are the same as those for the thermal expansion effect.
Piezoelectric effect. A thirdrank polar tensor property expressing the rate of change of polariza
tion with stress whose coefficients are the same as the firstorder electrostrictive effect.
Piezomagnetic effect. An axialmagnetic, thirdrank tensor property expressing the rate of change
of magnetization with stress whose coefficients are the same as the firstorder magnetostrictive effect
and with partial inherent symmetry due to their symmetrical stress and strain tensors, respectively.
Piezooptical effect. A linear or quadratic effect that expresses the rate of change of the dielectric
impermeability tensor with the stress tensor.
Piezothermoelectric power effect. The partially symmetrical, fourthrank, polar tensor property
that expresses the rate of change of the thermoelectric power tensor with the stress tensor and
whose coefficients are not all equal to those of the elastothermoelectric power effect.
Plane of symmetry. See mirror plane.
Point group. One or a set of macroscopic symmetry elements that contain a center of symmetry, a
mirror plane, a proper rotation axis of symmetry, or a combination of these that apply to one of the
32 crystal classes belonging to one of the seven crystal systems; a selfconsistent set of macroscopic
symmetry elements whose operations with respect to a given reference point restores that point to
its original position with the same handedness.
Poissons ratio. The ratio of lateral strain to longitudinal strain in simple tension or compression.
GLOSSARY OF TERMS AND EXPRESSIONS 217
Polarization. The total electric dipole moment per unit volume induced by the separation of
positive and negative electric charges produced by an external electric field.
Polar tensor. As used in this text, an ordinary Cartesian tensor whose components are neither
changed by a handedness change of the coordinate axes nor by the presence of a magnetic field; also
called a true tensor.
Positive current convention. The use of a positive test charge to determine the direction of elec
tric current flux.
Positive test charge. The + e  charge equal in magnitude to the charge on an electron.
Power series. As used in this text, an infinite series that is used to express a given function of one
or more variables, that is convergent within a finite interval, and for which all derivatives (or partial
derivatives) of the function are convergent within that interval.
Primary effect. Usually a firstorder (true) effect as opposed to a higherorder secondary (false)
effect.
Principal effect. A firstorder physical property or effect that relates conjugate parameters.
Proper choice of parameters. As used in this text, a requirement that all conjugate forceflux in
ner products have the same dimensions of entropy density production, s.
Proper rotation axis of symmetry. A onefold, twofold, threefold, fourfold, or sixfold rotation
axis.
Property. A physically measurable macroscopic characteristic of a thermodynamic system relating
cause and effect parameters.
Property compliance. In equilibrium thermodynamics, a physical property expressing the rate of
change of an extensive parameter with an intensive parameter.
Property rigidity. In equilibrium thermodynamics, a physical property expressing the rate of
change of an intensive parameter with an extensive parameter.
Pseudotensor. An axial tensor.
Pyroelectric effect. An independent coupled effect expressing the rate of change of polarization
components with temperature or the rate of change of entropy density with electric field strength,
as required by a Maxwell relation.
Pyromagnetic effect. An independent coupled effect expressing the rate of change of magneti
zation components with temperature or the rate of change of entropy density with magnetic flux
density, as required by a Maxwell relation.
Quadratic transformation form. A 6 6 or 9 9 transformation matrix derived from the trans
formation forms for a symmetrical or asymmetrical secondrank tensor, respectively.
Refractive index. See index of refraction.
Relative permittivity tensor. The ratio of the symmetrical polar secondrank permittivity tensor
to the permittivity in a vacuum (see dielectric constant).
218 TENSOR PROPERTIES OF SOLIDS
Reversible process. A process for which changes in the parameters that characterize the state of
a system return to the initial values in the reverse order by passing through a succession of equi
librium states.
Rhombohedral axes. An alternative set of axes sometimes used for the trigonal and hexagonal
crystal systems in place of the hexagonal axes used in this text.
RighiLeduc effect. See LeducRighi effect.
m m m
Righthand rule. The rule for the vector (cross) product V A sB is such that a righthanded
m m m
rotation about V carries A into B through an angle Fthat is not greater than 180o. As used in this
m m m m
text, the three vectors A , B , and A sB are mutually orthogonal where F90o.
Rigidity matrix. A property matrix generated from the equations of state for which the inten
sive parameters are given as functions of the extensive parametersthe inverse of the compliance
matrix.
Rotoinversion axis. An operation in crystallography involving a permissible nfold rotation fol
lowed by inversion through a center of coordinates.
Rule of subscript order. As used in this text, the rule by which the subscripts are read from top to
bottom and from left to right (hence, reading order) in a tensor differentiation operation.
Scalar gradient. A vector denoting the maximum rate of change of a scalar field and directed
along the direction of maximum change.
Scalar product. The limit of tensor contraction when the product between two tensors yields a
tensor of rank 0.
Schoenflies symbols. A symbology used to represent the symmetry elements characteristic of each
crystal class as an alternative to the HermannMauguin International Short System used in this text.
Secondary (false) effect. Usually of higher order than its corresponding primary effect but may
be caused by influences different from those causing the primary effect and that may serve as a cor
rection term to the primary effect.
Seebeck effect. The production of an opencircuit voltage, or thermoelectric electromotive force, be
tween two dissimilar conductors held at different temperatures under zero electric current conditions.
Self symmetry. The symmetry possessed by property coefficients that lie along the leading diago
nal of a property matrix.
Shear modulus. In simple shear, the ratio of shear stress to shear strain; the same as the modulus
of rigidity.
Skewsymmetrical tensor. See antisymmetrical tensor.
Space group. One of 230 selfconsistent arrangements of symmetry elements, perhaps over and
above those of a point group, that can bring a given crystal lattice into selfcongruence.
Space lattice. The atomic arrangement in a crystal represented as a threedimensional network
of straight lines.
GLOSSARY OF TERMS AND EXPRESSIONS 219
Specific heat. As used in this text, the heat capacity per unit volume.
State function. A thermodynamic property that depends on the state of the solid independent of
the path taken to reach that state.
Stereogram. A twodimensional depiction of a point group showing the relationship of all three
crystallographic axes.
Strain. The deformation resulting from the application of a generalized stress on the surface of
a solid such that the product of a generalized strain and stress results in the elastic strain energy
of the solid.
Strain gage effect. The piezoresistance effect.
Stress. A quantitative expression of the external force applied to a unit area of a condensed me
dium but which can also arise from internal inequalities in temperature distributions or by an iso
metric temperature change.
Subscript order rule. See rule of subscript order.
Sum rule. A generalization of Cartesian tensor summation that is restricted to tensors of the
same rank and tensor character.
Symmetric tensor. A tensor character expressed by the interchange of an even number of sub
scripts, used to represent tensor rank, without altering the values of the components.
Symmetry element. One of several symmetry operations that include a center of symmetry, a
mirror plane, a proper rotation, or rotoinversion axis of symmetry that apply to one of the 32 crystal
classes belonging to one of the seven crystal systems.
Symmetry operator. See generation operator.
Symmetry transformation. The operation on a property tensor by a generating matrix.
Taylors series expansion. A convergent power series of a function over a finite interval in which
all derivatives or partial derivatives of the function must exist and be continuous in that interval.
Temperature gradient. The gradient of the scalar temperature field T (for absolute temperature),
represented by the symbols grad T = T , and pointing in the direction of maximum T.
Tensor. As used in this text, an abstract quantity that is used to study the physical laws of nature,
classified by tensor rank r, specified by 3(r) components in threedimensional Euclidean (Cartesian)
space, and conforms to a specific transformation law.
Tensor character. The character inherited by its component or defining tensors and may be either
cumulative (by addition) or reductive (by cancellation).
Tensor contraction. Tensor contraction occurs when any n subscripts in the product of two ten
sors of rank rA and rB are set equal resulting in a tensor of rank rR (rA + rB)2n, where 2n b rA + rB.
Tensor field. As used in this text, a physical entity or rank r that is specified by 3(r) continuous
functions of position (x1, x2, x3) in threedimensional rectangular Cartesian space and accordingly
called a Cartesian tensor field.
220 TENSOR PROPERTIES OF SOLIDS
Tensor isomer. As used in this text, any tensor for which there is partial symmetry in its
subscripts.
Tensor operator. A generalized operator uijk ... of the nth order that is used to operate on a field
tensor, the most common being the vector operator ui used to yield the gradient of a scalar field
and the divergence of a vector field symbolized by ui F or grad FF and ui Yi o r d iv YY
respectively.
Tensor property. A physical entity that gives the rate of change of an effect tensor parameter
with a cause tensor parameter that, in general, varies with direction in a crystal system.
Tensor rank. The total number of subscripts (suffixes) associated with a tensor.
Tetrad. In crystallography, a fourfold (90o) rotation axis of symmetry.
Thermal conductivity. The secondrank, polar tensor transport property that relates a heat cur
rent density (flux) to a temperature gradient as in Fouriers law.
Thermal expansion. A symmetrical, polar, secondrank tensor property expressing the rate of
change of elastic strain with temperature and whose coefficients are the same as those for the pi
ezocaloric effect.
Thermal resistivity. The inverse of the thermal conductivity tensor.
Thermo. A prefix that usually denotes the influence of temperature change on a physical property.
Thermocouple effect. The Seebeck effect.
Thermodiffusive effect. Any effect that results from the simultaneous flow of heat and mass.
Thermodynamic equilibrium. A system is in thermodynamic equilibrium if it is simultaneously
in electrical, mechanical, thermal, and chemical equilibrium, such that all thermodynamic poten
tials are constant throughout the system and are the same as those of the surroundings. Thus, the
entropy production must be zero for such a system.
Thermodynamic potential. The result of a Legendre transform of the Euler relation that re
places one or more of the extensive parameters by their conjugate intensive parameters.
Thermodynamic tensor symmetry. Applied to the components of the general property compli
ance and rigidity matrices, it is the selfsymmetry of the principle effects and the symmetry ex
pressed by the Maxwell relations as derived from the application of Greens theorem in a plane and
the independence of the path principle.
Thermoelectric effect. Any effect that results from the simultaneous flow of electricity and heat.
Thermoelectric heater. A result of the Peltier effect whereby heat is issued to the surroundings
from the junction between two dissimilar conductors or semiconductors supporting an electric
current.
Thermoelectric power. The rate of change of the electrostatic potential with temperature under
opencircuit conditions (zero electric current) when dissimilar conductors are held at different
temperatures.
GLOSSARY OF TERMS AND EXPRESSIONS 221
Thermoelectric refrigerator. A result of the Peltier effect whereby heat is absorbed from the
surroundings by the junction between two dissimilar conductors or semiconductors supporting an
electric current.
Thermogalvanomagnetic effect. A transverse effect that results when electric current flows in
the simultaneous presence of an electric field, weak magnetic field, and a temperature gradient but
in the absence of mechanical stress and chemical potential gradients.
Thermomagnetic effect. One of several effects that results from the application of a temperature
gradient perpendicular to a magnetic field and producing either a transverse electrochemical potential
gradient or a transverse temperature gradient. Examples are the Nernst and LeducRighi effects.
Thermooptical effect. A linear firstorder or quadratic secondorder effect expressing the rate
of change of the dielectric impermeability tensor with temperature.
Thermostatics. See thermodynamic equilibrium.
Thomson effect. The interchange of heat between the surroundings and a uniform homogeneous
conducting material carrying both an electric current and a heat current.
Thomson heat. The heat that is interchanged with the surroundings during a Thomson effect
process.
Time reversal (inversion). A nonspatial symmetry operation that represents the quantum me
chanical spin magnetic moments, such that reversal of these magnetic moments with current re
versal correspond to time reversal (inversion).
Trace of a tensor. The sum of the diagonal components of a tensor represented by a square matrix.
Transport property. Any one of a host of properties that arise from irreversible thermodynamic
arguments.
Transpose of a matrix. A matrix obtained from a given matrix by the interchange of its rows and
columns, that is, by replacing the element Aij by Aji .
Triad. In crystallography, a threefold (120o) rotation axis of symmetry.
Trigonal system. One of three uniaxial crystal systems.
True effect. Usually a firstorder or primary effect for which a secondary (false) effect may appear
from influences different than those of the primary effect and serving as a correction to the true effect.
True tensor. Same as polar tensor.
Uniaxial crystal. A crystal for which two of the principal property components of a secondrank
tensor are the same the third being its optic axis that cannot have double refraction.
Unitary matrix. A square matrix which when multiplied by its complex conjugate transpose yields
the identity matrix.
Unit cell. In a crystal having an orderly (periodicity) arrangements of atoms, a singleunit paral
lelepiped can be identified from which the entire crystal can be imagined to be constructed by close
stacking of such units in three dimensions.
222 TENSOR PROPERTIES OF SOLIDS
Unit (identity) matrix. A square matrix for which the leading diagonal components are +1, all
others being zero.
Verdet coefficient. The proportionality constant used in the expression for Faraday rotation angle.
Youngs modulus. In a rod of an isotropic solid under uniaxial tension, the ratio of the longitudi
nal stress to strain in that longitudinal direction.
223
I Intensive parameter; bodycentered lattice; electric current; total magnetic dipole moment
Im Total magnetic dipole moment; intensive parameter
J Joules of energy; generalized ux
n
J Electric current density
q
J Heat current density
Ji Flux (current density) vector
Kij Dielectric constant (relative permittivity) tensor; generalized conductivity
kij Thermal conductivity tensor
l Length (e.g., in meters, m)
AB
L Phenomenological coefcient
m Plane of symmetry (mirror plane); meters
mijk Dependent magnetoelastic tensor
mijkl Magnetoelectrooptical tensor
Mi Total magnetic dipole moment per unit volume (magnetization)
n Refractive index
n Refractive index in the absence of all external elds
N Mole number; newton
Pijkl Elastooptical tensor
Pijkl Piezoresistance tensor
P Primitive lattice
P Total electric dipole moment
Pi Total electric dipole moment per unit volume (polarization)
Qijk Piezomagnetic tensor
Qijkl Piezomagnetoelectric tensor
rij Thermal resistivity tensor
rijk Linear electrooptical tensor; thermoelectrooptical tensor
R Hall constant; rhombohedral lattice; gas constant
Time inversion (reversal) operator
Rmn General property rigidity coefcient
Rijk Hall tensor
Rijkl Quadratic electrooptical (Kerr effect) tensor
S Entropy
s Entropy density
s(n) The nth generating matrix used to determine crystal symmetry effects on tensor properties
s Entropy density production
sijkl Elastic compliance tensor
GLOSSARY OF SYMBOLS AND ABBREVIATIONS 225
Greek Symbols
A Quadratic transformation form for symmetrical secondrank tensors; an intensive parameter
Aij Thermal expansion tensor
B Quadratic transformation form for asymmetrical secondrank tensors; an intensive
parameter
Cij Dielectric susceptibility tensor
Dij Kronecker delta
Eij Elastic strain tensor
Eijk Ettingshausen tensor; dependent electroelastic effect tensor
F Scalar eld potential; a thermodynamic potential
Gij Magnetoelectric susceptibility tensor; Grneisen tensor
Gijkl Secondorder electrostrictive tensor
Hi Dependent magnetocaloric tensor
Hijk Nernst tensor
K Permittivity in a vacuum
M Permeability in a vacuum
Mc Chemical potential
?
M Electrochemical potential (Fermi level in equilibrium state)
N Poissons ratio
Uij Dependent magnetoelectric tensor
Pijkl Linear piezooptical tensor; thermopiezooptical tensor
ij Peltier tensor
ijkl Piezothermoelectric power tensor
ijklmn Quadratic piezooptical tensor
QF Faraday rotation angle
Rij Resistivity tensor
Rijkl Magnetoresistance tensor
Rijklmn Piezomagnetoresistance tensor
Sij Electrical conductivity tensor; stress tensor
S(n) Quadratic form of s(n)
ij Thermoelectric power tensor
228 TENSOR PROPERTIES OF SOLIDS
Author Biography
Richard F. Tinders teaching interests have been highly variable during his tenure at Washington
State University. They have included crystallography, thermodynamics of solids (both equilibrium
and irreversible thermodynamics), tensor properties of crystals, dislocation theory, solidstate direct
energy conversion (mainly solar cell theory, thermoelectric effects, and fuel cells), general materials
science, advanced reaction kinetics in solids, electromagnetics, and analog and digital circuit theory.
In recent years, he has taught logic design at the entry, intermediate, and advanced levels and has
published a major text, Engineering Digital Design, on that subject. He has conducted research
and published in the areas of tensor properties of solids, surface physics, shock dynamics of solids,
millimicro plastic ow in metallic single crystals, highspeed asynchronous (clockindependent)
state machine design, and Boolean algebra (specically XOR algebra and graphics). Most recently,
Prof. Tinder has published an ebook, Relativistic Flight Mechanics and Space Travel (Morgan &
Claypool Publishers, 2007). Prof. Tinder holds bachelor of science, master of science, and doctor of
philosophy degrees, all from the University of California, Berkeley.
He has spent one year as a visiting faculty member at the University of California, Davis, in
what was then the Department of Mechanical Engineering and Materials Science. Currently, he is
professor emeritus of the School of Electrical Engineering and Computer Science at Washington
State University where he has been a major contributor to the computer engineering program there
during a period of nearly two decades.
231
Index
Hexagonal crystal system, 42ff, 51ff, 55, 59, Maclaurin series expansion, 31, 109, 213
99ff, 114 Magnetic eld strength, 175ff, 213
Higher order magnetotransport properties, 186ff Magnetic ux density, 66, 213
Holohedral groups, 46, 49, 52ff, 211 Magnetic point groups, 38, 57, 187, 193, 213
Hookes law, 110ff, 211 Magnetic susceptibility, 75, 213
Magnetization, 62, 64, 67, 91, 213
Identity matrix, 47, 211 Magnetocaloric effect, 7, 76, 214
Independent of path principle, 72, 211 Magnetoelectric susceptibility, 7, 77, 214
Independent variable, 6, 212 Magnetoelectrooptical effect, 132
Index of refraction, 129, 130, 139, 141, 212 Magnetooptical effects, 131, 214
Indicatrix, 130, 136, 212 Linear, 131, 139, 141, 142
Inexact differential, 61, 212 Quadratic, 131, 139ff
Inner product, 26, 27, 212 Magnetoresistance, 181ff, 186, 214
Intensive parameter, 3, 5ff, 61ff, 212 Magnetothermoelectric power effect, 186ff,
Interaction diagram, 5ff, 212 214
Interaction effect, 87ff, 212 Magnetic dipole moment, 62, 64, 67, 190
Inverse of a matrix, 22, 212 Markoff process, 150, 151, 214
Irreversible process, 5, 9, 10, 147, 150ff, 212 Matrices
Isentropic process, 78, 80, 82, 212 Determinant of, 22, 29
Isometric, 85, 89, 91, 212 Inverse, 16, 21, 22, 212
Isopiestic, 9, 212 Jacobian, 32
Isothermal condition, 9, 64, 78ff, 113, 162ff, Square, 20
172, 178ff, 212 Trace, 28, 33, 221
Isotropic solid, 115, 118ff, 213 Transpose, 16, 18, 21, 22, 221
Unit, 222
Joule heat, 156, 164, 165, 213 Maxwell relations, 65, 72ff, 80, 85ff, 127, 214
Method of direct inspection, 4748, 52ff, 99ff,
Kelvin relation, 163ff, 213 114, 214
Kerr effect, 131ff, 213 Microscopic reversibility, principle of, 150, 151
Kronecker delta, 26, 31ff, 36, 164, 213 Miller indices, 41ff, 214
Generalized, 36 MillerBravais indices, 42, 214
Substitution property of, 34 Mirror plane, 39, 40, 214
Modulus of rigidity, 120, 122, 215
Lattice parameter, 42, 213 Mole number, 172, 215
LeducRighi effect, 177ff, 185ff, 213 Monad, 38, 215
Legendre transform, 63ff, 213 Morphic effect, 123, 124, 215
234 TENSOR PROPERTIES OF SOLIDS
Secondary (false) effect, 133, 134, 143, 218 Tensor gradient, 31, 32
Seebeck effect, 159, 163, 169, 218 Tensor isomer, 21, 220
Self symmetry, 73, 75, 85, 218 Tensor operator, 31, 32, 220
Shear modulus, 122, 218 Tensor property, 3, 4, 9, 89, 95, 185ff, 220
Skewsymmetrical tensor, 218 Tensor rank, 13, 24ff, 29, 32, 35, 220
Space groups, 38, 218 Tensors, Chapter 2
Space lattice, 38, 41, 42, 190, 218 Antisymmetrical, 14, 17ff, 29, 34, 205
Specic heat, 74, 219 Asymmetrical, 14, 20, 25, 32, 205
State function, 72, 219 Axial, 13ff, 26, 2930, 205
Stereogram, 105, 201, 219 Axialmagnetic, 13, 14, 30, 183, 205
Stokes theorem, 72 Differentiation of, 30, 31
Strain gauge effect, 169, 170, 219 Dual of, 35, 192, 208
Stress, 95ff, 110ff, 219 Magnetic, 29, 30, 182, 185, 213
Biaxial, 97 Partially symmetrical, 14, 22, 23, 27, 215
Compressive, 97, 105 Polar, 15, 16, 25ff, 189, 191, 193, 217
Hydrostatic, 97 Principal components of, 18, 24
Shear, 97, 105 Symmetrical, 17ff, 30, 219
Uniaxial (tensile), 97, 105 Transformation of, 14ff
Sum rule, 26, 219 Tetrad, 38, 220
Symmetrical tensor, 17ff, 30, 52, 74ff, 140, 219 Thermal conductivity, 149, 157, 179, 184ff,
Symmetry operator, 49, 56, 219 220
Symmetry transformation, 37ff, 52ff, 219 Thermal expansion, 3, 4, 7, 9, 76, 81, 89, 220
Thermal resistivity, 158, 220
Taylor series expansion, 31, 66, 68, 123, 125, Thermocouple effect, 159ff, 220
183ff, 219 Thermodiffusive effect, 171ff, 220
Temperature gradient, 10, 149, 159, 164, 171, Thermodynamic equilibrium, 61ff, 151, 220
219 Thermodynamic potential, 62ff, 71, 75, 85, 220
Tensor algebra, 2529 Thermodynamic tensor symmetry, 220
Addition, 26 Thermoelectric effects, 159ff, 171, 220
Contraction, 27 Thermoelectric heater effect, 162163, 220
Multiplication, 26 Thermoelectric power, 160ff, 176, 183ff, 220
Outer product, 27 Thermoelectric refrigerator effect, 162163,
Tensor character, 26ff, 35, 188, 219 221
Tensor contraction, 2729, 219 Thermoelectrooptical effect, 131
Tensor differentiation laws, 30, 31 Thermogalvanomagnetic effects, 184185,
Tensor elds, 3136, 219 221
236 TENSOR PROPERTIES OF SOLIDS
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