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SOLID STATE PHYSICS: CRYSTAL STRUCTURE


Introduction:
We know that elements and chemical compounds occur in three states
viz., gas, liquid and solid.
Solids are broadly classified as Crystalline, polycrystalline and
Amorphous depending on the extent to which atoms or molecules are arranged in a
regular, periodic manner.
Crystalline solids have a regular geometrical shape. This regular shape is a
manifestation of the regular, periodic arrangement of atoms, or molecules, which
make up the solid. In a crystal, the atoms or molecules are arranged in a regular and
periodic pattern. When this periodic arrangement of constituent particles extends
throughout the solid, it is known as a ‘single crystal’. There is a long range order
throughout the single crystal.
A polycrystalline solid is an aggregate of many small crystals separated by
well-defined boundaries; the orientations of the adjacent single crystals across these
boundaries are random. In other words, the orientation of the periodic arrangement
of atoms in adjacent small crystals of the polycrystalline solid is changed abruptly
into an arbitrary orientation at these boundaries. Though crystal grains are small,
there is a long range order of atomic arrangements within each crystal grains.
In an or molecules are not arranged in a regular fashion they are said to be
‘amorphous’. When the atoms, molecules, or ions of a solid are arranged in a
regular and periodic pattern, they are called ‘crystalline’.
In a crystal, each atom or ions are bound to each other more strongly
than in liquids and gases. The interatomic distances between them are smaller than
that in liquids and gases. The study of the ‘solid state physics’ aims to interpret the
macroscopic bulk properties of a solid in terms of its constituent microscopic
particles.
CRYSTAL STRUCTURE:
A crystal is a three dimensional body made up of a regular array of
atoms (or ions) in all directions. It is called as the ‘crystal structure’. The crystal
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structure may be defined in terms of an idealized geometrical concept called ‘space


lattice’. It is an array of points in space such that the environment about each point
is the same. A three dimensional space lattice may be defined as an infinite array of
points in three dimension in which every point has an identical environment as any
other point in the array.
EXAMPLE:
Consider the points shown in the diagram, which represent a two
dimensional space lattice.
Along the X-axis, distance between each constant points is ‘a’, while
along Y-axis it is ‘b’. This can be extended infinitely along both x and y directions.

Y-axis . . . . . . . .
. . . . . . . .
. . . . . . . .
b . . . . . . . .
b . . . . . . . .
a a
X- axis

If it is extended infinitely in the Z direction also with a spacing of C (say),


then it represents a three dimensional array.
Extension of atoms in any or all direction is by the repeated movement in
steps of a particular unit. For example, here at every distance of ‘a’ along x axis we
have an atom. The repeated movement is called ‘translation’. A translation can be
represented by a vector.
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→ → →
In the figure translational grid lines a , b , c are three non-coplanar
ranslational vectors. By repeated action (i.e., translational), they are sufficient to
→ → →
repeat the origin at every point in the ‘space lattice’. These a , b , c vectors are
known as ‘three unit translations’.
THE BASIS:
Every lattice point in a crystal structure is associated with one or more atoms
or ions called the ‘basis’. When the basis is repeated with correct periodicity in all
directions, it gives the actual crystal structure. In a crystal, the basis is identical in
composition, arrangement, and orientation. The basis can be mono atomic (Na, Fe
etc), diatomic (KCl), triatomic (Ca F2) etc.

. . . . .. .x .x .x .x
. . . . . .x .x .x .x
. . . . . .x .x .x .x

a c a c a c a c a c a c
b b b b b b

a c a c a c a c a c a c
b b b b b b
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Thus in general, when the basis is repeated in the lattice, crystal structure is
obtained.
UNIT CELL:
Consider a two dimensional space lattice. Construct a parallelogram with
sides ABCD, AB = a and AD = b. by translating (i.e, by shifting) the parallelogram
by any integral multiples of vector a and b, the whole crystal structure may be
obtained in two dimensions. This can be extended to three dimensions also. The small
parallelepiped built upon the three translations selected as unit translations is known
as the ‘unit cell’.
The unit cell, though imaginary, has an actual shape and a definite minimum
volume. The entire crystal structure is obtained by the geometrical repetition of the
unit cell.

. . . . . .. . . .
. . . . . . . . .
. . . . . . . . .
. . . . . .. . . .
. . . . . . . . .
. . . . . . . . .

It must be noted that the choice of unit cell is not unique. For example,
consider parallelogram PQRS in the above diagram. By shifting this appropriately the
crystal structure can again be obtained. Therefore this can also be considered as a unit
cell. However if the unit cell of a crystal occupies a minimum volume, then it is
called as ‘primitive cell’.
A primitive unit cell has lattice points only at the corners of the unit cell.There
are no additional atoms at the interior of the unit cell or on the faces of the unit cell.
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A ‘non-primitive unit cell’ has additional lattice points at the Face centres or at Body
centre in addition to the corner points.
→ → →
The volume of the primitive cell is given by | a x b . c | . A primitive cell
may be constructed by the following way.
1. Draw lines to connect a given lattice point to all the nearby lattice
points.
2. At the mid point and normal to these lines draw new lines or planes.

The smallest volume enclosed in this way is called a primitive cell. This
method is due to WINGNER and SEITZ.

two dimensional view

In general, the unit cell may be defined as the smallest volume of a crystal from
which the entire crystal may be constructed by translational repetition in three
dimension.

PRIMITIVE LATTICES AND BRAVAIS LATTICES:


(a) PRIMITIVE LATTICE:
→ → →
The lattice and the translational vectors a ,b , c are said to be primitive if any two

points r and r ' , from which the atomic arrangement looks the same, always satisfy the relation
→ → →
r ' = r + n1 a + n2 b − n3 c where n1,n2 and n3 are suitable integers.

Seven Crystal Classes: (primitive)


It is found that there are seven systems of primitive lattices with lattice points
only at the corners of the unit cell. They are classified on the basis of the lengths
→ → →
( i.e, translational vectors a , b , c ) and directions of the axis of the symmetry

(i.e, angles α , β , γ between the axes) as given below. It should be noted that ,
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γ is the angle between a and b ;


→ →

α is the angle between b and c


→ →
;

β is the angle between a and c


→ →
;

b

α γ a

→ β
c

The seven systems of the crystal classes are


i. Cubic ii.Tetragonal iii Orthorhombic
iv. Rhombohedral v. Hexagonal vi. Monoclinic
vii. Triclinic

BRAVAIS LATTICES:
In 1848, Bravais showed that there are only 14 ways of arranging points in
space, so that the environment looks the same from each point. In the primitive
lattices, lattice points are considered only at the corners of the unit cell. But in the
monoclinic, orthorhombic, tetragonal and cubic systems, there are also seven other
lattices which have more symmetry than the primitive lattices. In these seven
additional types, there are faces or at the body diagonal in addition to those at the
corners. These seven types of lattices are known as centered lattices. Thus totally, 7
primitive type + 7 centered = 14 type of crystal lattices are there. These are known as
Bravais lattices. All these fourteen types are conventionally grouped into seven
systems according to the conventional unit cells.
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System No. of Lattice Restriction Example


lattices symbol On convention cells

Cubic 3 P(sc) a=b=c α -Po


I(bcc) α = β = γ =90
F(fcc) Na, W, Ag, Au, Pb

Trigonal 1 P a=b=c Calcite


α = β = 90 ≠ γ
γ < 120
Tetragonal 2 P,I a=b ≠c Indium
α = β = γ =90

Orthorhombic 4 P,C,I,F a≠b≠c


(C=base- α = β = γ =90 Olivine
centered) Mg 2 SiO4

Hexagonal 1 P a=b ≠c Quartz, Zn, Cd


α = β = 90 ≠ γ
γ = 120
Monoclinic 2 P,C a≠b≠c Borax,CaSO4.2H2O
α = γ = 90 ≠ β

Triclinic 1 P a≠b≠c K2Cr2O7


α ≠ β ≠γ

. 1. CUBIC LATTICE: ( 3 types, P, I and F)

There are three types of cubic lattices namely, simple cubic (sc), body centered
Cubic (bcc), face centered cubic (fcc).
a. Simple cubic or Primitive cubic (Sc) (cubic P):
There is one lattice point at each of the eight corners of the unit cell and there
is no lattice point inside the unit cell. Thus the primitive cell of SC (which is primitive to other cubic
systems, too) consists of only one lattice point.
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b. Fcc (Face Centered Cubic) (cubic F):


There is one lattice point at each of the eight corners and one lattice point at each of the six
faces of the cubic cell. Thus an fcc consists of a 4 lattice points.
c. Body centered (Bcc) (cubic I):
There is one lattice point at each of the eight corners and one lattice point at the body centre of
the cell. Thus a Bcc consists of 2 lattice points.

2.TRIGONAL: (I)
Here a Rhombohedron is chosen as the primitive cell. This lattice itself is primitive.
3.TETRAGONAL: (2 types, P and I)
Here the simple unit cell is a right square prism. A second tetragonal lattice type is body
centered.
4. ORTHORHOMBIC: (4 types, P, C, I and F)
In this system there are four types of lattices, namely 1.primitive(P), 2.base centered( C)
3.body centered (I) and 4. face centered (F).
5.HEXAGONAL:(I)
The conventional cell chosen is a right prism based on a rhombus with an angle of 600 .
The lattice is primitive.
6.MONOCLINIC: (2 types, P and F)
There are two types. 1. primitive cell (P) and 2. face centered (F) with lattice points at the
centers of the rectangular faces in the ab plane.
7. TRICLINIC: (I)
This is a primitive cell. It consists of three axes of unequal lengths and unequal angles.

NUMBER OF ATOMS PER UNIT CELL in Cubic Lattices


SIMPLE CUBIC (P) LATTICE
There are eight atoms at the eight corners of the cube. Each corner atom is shared by eight
adjacent unit cells surrounding that atom. Therefore only 1/8th of an atom belongs to a given unit cell.
1
∴ Contribution from all the 8 corner atoms to one Simple Cubic unit cell = 8 x = one atom.
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∴ TOTAL NUMBER OF ATOMS/ UNIT CELL OF SIMPLE CUBIC LATTICE = 1 ATOM.
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B.C.C. ( I LATTICE)
There are eight atoms at eight corners of the cube and one atom at the body centre of the
cube. Each corner atom is shared by eight unit cell.
1
∴ Contribution to one unit cell from all the corner atoms = 8 x = one atom
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In addition to this, each unit cell has one atom at the body center which belongs to that unit
cell completely.
∴ Total number of atoms in a BCC unit cell =1+1= 2 atoms.

F.C.C. ( F LATTICE)
It consists of 8 atoms at eight corners of the cube + one atom at the centre of each of the six
1
cube faces. Contribution from corner atom/cell = 8 x = one atom
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Each face centered atom is shared by two adjacent unit cells.
1
∴ Contribution from face centered atoms = 6 x =3 atoms
2
∴ Total number of atoms/unit cell = 1+ 3 = 4 atoms.
---------------------------------------------------------------------------------------------------

COORDINATION NUMBER:
Every atom in a crystalline structure is surrounded by other atoms. The number of equidistant
nearest neighbors that an atom has in a given crystal structure is called the ‘coordination number’.
When the coordination number is large, the crystal structure is more closely packed.
COORDINATION NUMBER:
The number of equidistant nearest neighbor atoms that a given atom has in a given crystal
structure is known as ‘coordination number’.
If the atoms of a crystal lattice are assumed to be hard spheres arranged in a repeated regular
pattern, a given atom will touch all its nearest neighbor atoms.
ATOMIC RADIUS:
When any two identical spheres touch each other, the distance between their centers will be
equal to twice their radius.
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Hence, atomic radius may be defined as half the distance between any two nearest neighbor
atoms in a given crystal structure.

PACKING DENSITY (or) ATOMIC PACKING FACTOR:

A cubic unit cell of edge ‘a’ has a volume a 3 . If the lattice points of a unit cell are assumed to
be occupied by spherical atoms at corners, and body or face centers, the entire volume of the unit cell
is not occupied by the lattice atoms.
The atomic packing factor (or packing density) is defined as the ratio of total volume
occupied by the atoms or molecules in a unit cell to the volume of the unit cell.
Total volume occupied by atoms in a unit cell
i.e. Atomic Packing Factor = ------------------------------------------------------
Volume of the unit cell.

(no. of atoms/unit cell) . (Volume of one atom)


= ------------------------------------------------------
volume of the unit cell

COORDINATION NUMBER FOR SC, BCC, AND FCC:


¾ SIMPLE CUBIC: A simple cubic lattice has atoms at eight corners only. Each corner
atom is surrounded by 4 other corner atoms in a horizontal plane. In addition to this, there is one atom in a
plane above this plane and another atom in a plane below this. So there are six nearest neighbors to an
atom in a simple cubic lattice. They lie along the cube edges.
¾ FACE CENTERED CUBIC: A FCC unit cell has eight corner atoms as well as an atom

at the centre of each of the six cubic faces. The nearest neighbors of a corner atom are the face centered
atoms surrounding it and vice versa.
In a given plane (say XY plane) containing the given corner atom O, it has
four nearest neighbor face centered atoms in the four adjacent unit cells. Similarly, when we consider the
other two perpendicular planes (say, XZ and YZ planes) containing the atom O, it has four more nearest
neighbors in each of these two planes. Hence totally, there are 12 nearest neighbor face centered atoms to
a corner atom. In a similar manner it can be shown that there are 12 nearest neighboring corner atoms to
each of the face centered atoms. So coordination number for FCC is 12.
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¾ BODY CENTERED CUBIC: In a BCC structure, in addition to the eight corner atoms, there is
a body centered atom along the body diagonal. Each body centered atom is surrounded by eight nearest
neighbor corner atoms and vice versa. Hence coordination number for a BCC structure is 8.
___________________________________________________________________________________

Calculation of Atomic Radius in terms of Lattice Constant.


1. The simple cubic lattice: The front view of a simple cubic lattice is shown fig.

2r There are eight atoms per unit cell situated at the eight corners. If a is the
side of the unit cell and r be the radius of the atom, then from fig.,
a
2r = a or r =
2
2. Body centered cubic (bcc) lattice: In the unit cell of bcc lattice there are eight atoms
at corners each forming a member of eight cells and one atom per cell at the body centre. The
calculation of r can be made with the help of fig. From the figure, the nearest neighbors of a body
centered atom lie along the body diagonal, DF (say). If ‘a’ is the cube edge, then AB= AD = BF = a and
DF = 4r; where r is the atomic radius.
In ∆ABF, AF = √[ (AB)2 + (BF)2 ] = √ ( a2 + a2 ) = a√2

H G

A F
B
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In ∆ADF,
DF 2
= ( DA ) 2 + ( AF ) 2
(4 r )2 = a 2 + (a 2 )2
( 4 r ) 2 = 3 .a 2
3
r = a
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3. Face centered cubic (fcc) lattice: In the face centered cubic lattice, there are eight corner atoms
in the unit cell and one atom at the centre of each face. Fig. shows the front view of fcc structure unit
cell while fig shows its cut view.
From the fig we have the nearest neighbour of a Face centered atom lie along the Face
centered DB. If r is the atomic radius,
B
A

D C

DB = 4r
( BD ) 2 = ( DC ) 2 + (CB ) 2
i.e, ( 4r ) 2 = a 2 + a 2

= 2a 2
2
r = .a
4
4
(or) a = r
2
a = 2 2r
------------------------------------------------------------------------------------------------------
PACKING DENSITY (or) PACKING FACTOR:

Packing density or packing factor is defined as the ratio of the volume of the atoms per unit cell to
the total volume of the unit cell.
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Total volume occupied by atoms in a unit cell


i.e. Atomic Packing Factor = ------------------------------------------------------
Volume of the unit cell.

(No. of atoms/unit cell). (Volume of one atom)


= ------------------------------------------------------
volume of the unit cell
If n be the number of atoms in a unit cell each with radius r and if a be edge of the cubic unit cell,
3
⎛ a ⎞
3
4 ⎛ 3 ⎞
⎜ ⎟ π 2 × π ⎜ .a ⎟
3 ⎝ 4 ⎠ = 3π =
then the packing factor (APF) = ⎝ 3 ⎠ = =
2 2
a 6 a3 8
Here we shall calculate the packing density in the following cases:
(1) Simple Cubic Lattice:
Number of atoms per unit cell, n=1
Atomic radius r in terms of cube edge a is r = ( ½ )a
(No. of atoms/unit cell). (Volume of one atom)
Atomic Packing factor = ------------------------------------------------------
volume of the unit cell
3
4 4 ⎛a⎞
n × π r3 1× π ⎜ ⎟
3 3 ⎝ 2⎠ π
i.e., APF = = = =
a3 a3 6

(2) Body Centered Cubic Lattice:


Number of atoms per unit cell, n=2
3
Atomic radius r in terms of cube edge a is r= a
4
3
4 ⎛ 3 ⎞
4
n × π r3 2× π ⎜ .a ⎟
3 3 ⎝ 4 ⎠ 3
∴ APF = = = π=
a3 a 3
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(3) Face Centered Cubic:


Number of atoms per unit cell, n=4
⎛ a ⎞
Atomic radius r in terms of cube edge a is r= ⎜ ⎟
⎝2 2⎠
3
4 4 ⎛ a ⎞
n × π r3 4× π ⎜
3 3 ⎝ 2 2 ⎟⎠ π
∴ APF = = 3
= =
a3 a 3 2

Various properties of the cubic crystal structures are given below.


Name of Cubic Number of Coordination Atomic radius Atomic Packing
Unit Cell atoms/unit cell Number r Factor
Simple Cubic 1 6 a/2 π
6
Body Centered 2 8 3 3
a π
Cubic 4 8
Face Centered 4 12 ⎛ a ⎞ π
⎜ ⎟
Cubic ⎝2 2⎠ 3 2

Relation between lattice constant and density in cubic crystal systems


Let ‘a’ be the lattice constant (cube edge) of the cubic unit cell. Let ρ be the density.
∴ Volume of one unit cell = a3
Mass of one unit cell = volume x density = ρ.a3 ---------- (1)
Let there be n number of atoms or molecules per unit cell. If M be the molecular weight and N be the
Avogadro number, then,
Mass of each molecule (or atom) = M / N
∴Mass of one unit cell = number of atoms ( or molecules) per unit cell x volume of each
atom (or molecule)
nM
= -------------------- (2)
N
nM
Comparing eqns. (1) and (2) we have, ρ.a3 =
N
1 1
⎛ nM ⎞ 3 nM ⎛ nM ⎞ 3
i.e., .a3 =⎜ ⎟ (or) a = ⎜ ⎟
⎝ Nρ ⎠ Nρ ⎝ Nρ ⎠
With the help of the above equation, lattice constant a can be obtained.
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Miller Indices of Lattice Planes


The crystal structure may be considered as made up of a set of parallel, equidistant planes passing through
one or more lattice points. For a given crystal system these lattice planes may be chosen in different ways.
(Planes marked as A, A.., B,B.., C,C… etc. in the figure)
Miller devised a method to index the lattice planes of a crystal structure. The lattice planes of a
crystal structure are designated by three numbers, h, k, l within parenthesis.
The three numbers h, k and l are written within parentheses without commas between them as (hkl) are
known as Miller Indices and they represent a set of parallel planes.
Miller Indices of a lattice plane may be defined as the three smallest integers which have the same
ratio as the reciprocals of the intercepts of the plane on the three axes.
The procedure for finding the Miller Indices of a plane is described below.
To find the Miller Indices of Plane PQR,
1) Find the intercepts (n1a, n2b, n3c) of the plane on the three axes defined by the basis vectors, a, b,

and c.

2) Get the three numbers (or) coefficients of a, b, c, as n1 n2 and n3.


G G G
⎛ n1a n2b n3c ⎞
⎜ 1
n = G , n2 = G n3 = G ⎟
⎝ a b c ⎠

3) Find the reciprocals of these numbers; i.e., find 1/n1, 1/n2, 1/n3.
4) Multiply the reciprocals by their Least Common Multiplier (LCM). The resulting set of three
numbers h = (1/n1).LCM, k = (1/n2).LCM and l = (1/n3).LCM are written within
parenthesis as (hkl). (hkl) is called Miller Indices of the given plane.
Thus a plane satisfying the equation h : k : l = 1/n1 : 1/n2 : 1/n3 is said to have the
Miller Indices of (hkl).
Example:
To find the miller indices of a plane making intercepts 2a, 3b and 4c with the axes.
Intercepts of the plane on the three axes Æ 2a, 3b, 4c
Coefficients of intercepts = 2, 3, 4
Reciprocals of coefficients = ½, 1/3, ¼
LCM of reciprocals = 12
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∴ h = (1/2).12 = 6, k = (1/3).12 = 4, l = (1/4).12 = 3


∴Miller indices (hkl) of the given plane is (643)
Salient Features of Miller Indices:
1. The Miller Indices represents not a single plane but a family of parallel planes. (200) , (100) etc are
parallel planes and both can be represented by (100)
Similarly (111), (222) … etc are also a family of parallel planes. In general, (hkl) and (nh nk nl) = n
(hkl) for any n belong to a family of parallel planes.
2. If a plane cuts any of the three axes on the negative side of the origin, then, the intercept and hence
the corresponding Miller index for the axis will be negative. A negative Miller index is written
with a “bar” over it.
Thus in the above example, if the intercepts are 2a, 3b, -4c, then the corresponding Miller indices
would be h = 6, k = 4 and l = -3 and therefore, Miller Indices of the given plane is (6 4 3).
3. A plane parallel to a particular axis has an intercept of ∞ and hence the corresponding Miller index
would be zero. Thus Miller indices (100) of a plane mean that the plane is parallel to both y and z-
axes.
4. the normal to the plane (hkl) is the direction [hkl] within the crystal
5. The normal distance d between the adjacent neighboring planes of the family (hkl) in a cubic
a
crystal with cube edge ‘a’ is given by d= . d is the interplanar spacing.
( h2 + k 2 + l 2 )
--------------------------------------------------------------------------------------------------------
Reciprocal Lattice
The concept of reciprocal lattice was introduced by Ewald. A crystal may be considered as made
up of a number of interpenetrating lattice planes. These lattice planes can be represented conveniently by a
set of lattice points in a space known as ‘reciprocal space’. Vectors in reciprocal space have unit of length-1.
Let a, b and c be the basis vectors in direct lattice. The basis vectors a*, b* and c* of the reciprocal
lattice are defined by assuming the following:
a*.a = 2π; b*.b = 2π; c*.c = 2π …….(1)
a*.b = a*.c = 0; b*.c = b*.a = 0 and c*.a = c*.b = 0
These equations imply that the vector a* in reciprocal lattice is perpendicular to the plane containing both
the vectors b and c of direct lattice and so on. Thus a* is a vector perpendicular to the bc plane of the
direct lattice and so on. The basis vectors of the reciprocal lattice are defined using the above assumptions
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b×c c×a a×b


as a ∗ = 2π . b ∗ = 2π . c ∗ = 2π . …….(2)
a.b × c b.c × a c.a × b
The denominators of the set of equations (2) represent the volume of the unit cell.
The lattice points in a direct lattice are defined by the vector R from the origin as
R = n1a + n2b + n3c. ……..(3) Similarly, the reciprocal lattice points are given by the reciprocal lattice
vector G = ha* + kb* + lc*…….. (4) . Here, n1, n2 and n3 and h,k and l are integers; h, k, l are the Miller
indices of the plane (hkl).
Properties:
1. An important property of the reciprocal lattice is that the reciprocal lattice vector G= ha* + kb*
+ lc* is normal to the crystal lattice plane with Miller indices (hkl).
2. The spacing between adjacent (hkl) plane of the direct lattice is given by
d hkl = (n.2π) / |G| where n is an integer.
3. The direct lattice is the reciprocal of its own reciprocal lattice. The reciprocal lattice of simple
cubic is simple cubic; The reciprocal lattice of body centered cubic is face centered cubic and vice versa.
Significance and applications:
1. The orientations of different sets of direct lattice planes (two dimensional) are very conveniently
represented by one dimensional vectors in reciprocal space.
2. If K and K’ are the wave vectors of the incident and diffracted X-rays, and
if ∆K = K’-K, then it can be shown that the Bragg’s diffraction condition (2dsinθ=nλ) is satisfied when
∆K = G , where G is a reciprocal lattice vector.. Thus the concept of reciprocal lattice provides an easier
way of interpreting the X-ray diffraction data.
K K’
∆K = Ghkl
|K| = 2π / λ = |K’| θ θ . (hkl) plane
(for elastic scattering) θ
λ Æ wavelength of X-ray used for K
x-ray diffraction

3. The wave mechanical behavior of electrons in periodic crystal lattices is easily


understood in terms of the reciprocal lattice. This is because, the wave vector space (K
space) of the electrons in a crystal is periodic in reciprocal lattice.
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