as:,'

?tZ

-:.
:

Figure

A primitive cell nay also be chosen following

(1) draw lines to connrct a given lattici
poirt to all nearbv Iattice points;.(2) at tlie midpoint
arJ ncmal to tbese lines, draw new iines or plalai
The
snallest volume encjosed ia tlis way is tle liigner-Seitz
prnitire cell. -{i1 space mav be f;lled b1,these1els, jut
as bv the cels of Fig. 7.
..his orocedwe:

a Prirnitil'e cell is a minimum-vofu:E]e ceil.8 There is a densir)* of one

lattice
point per primitive ceil.s There aie iattice points at the eighi corners
of the
parailelepiped, but each corner point is shared among the eight
cells which
touch tlere. The volume !'" of a primitive cerl defined by primiuie a_res
a, b, c is

V"- la=b.cl ,
by elementary vector anall'sis. The basis
primiiive cell may be calied a

(3)

r+j& a lattice point of a

No basa conr"ins feiver atoms

associated

p::-a-:iu.,,e basis.

ttran a primiiive basis contains.

Alothe.*'ay of choosing a cel of equar
'oiume v" is shown in Fig. g.
The cer formed in this rvay is isro*'n to phy-sicrsts
as a \yigrrer-seitz primitir.e
cell.

FL\DA}fEI{IiL TI?ES OF L{IrICES1O

Crystal lattices .can be carried into themserves not on-ly by the rattice
T of Eq. (2). but also b'r'ariou-s poir,t srn:rmetry op"r"uonr. e
typical syrnmetry operation is tiat of rotation about an arcis which passes
through a latLice poirt. Lattices can be for:nd such fhaf 6s6_, tr,,,o_,
tluee_,
fo'r-, and six-fold rotation axes are permissible, corresponding to rotations
by
2n, 2r/2, %r/3, 2r/4, and 2r/6 ra&ans and by integral *ulUpl",
of these
rotations. The rotation axes are cienoted by the slmbof, f, S, 3,
+, and 6.
we cannot find a lattice that goes into itself under other rotations, such
a-sby 2tr/7 radians or 2n/s radiarrs. A single molecule can have
any degree of
rotational rymmetry, but an infinite periodic lattice cannot. We
can make a
crystal from molecu-tres which individually have a five.fold rotatioo
axis, but
we should not eryect the lattice to have a ffve-fold rotation axis.
rn Fig. ga.
what happens if we try to corrstruct a periodic lattice having ve1v3-show
fold symmetry: the peaiagons do not fit togetJ-rer neatly. we see
that *I ."otrarulations

There ae muvrvays
of crro;sngile

primiti'e ues ad primitive cen foragivenrattice(Fig.7a).

eThe nmtrer of atom in a pri:nitive
ell is the nmber
toT" origrnal i848 study by A- Bnvais is reprinted in hisof atoms in the bisis.
Erud6 crystalragraphigubs,

-.-,.
vill's' Pads, 1866; a cemm traslation appem io ostward's xtot"ixn

ceutier-

io ooi6-,rii:xarcrqtn

90' (f897). For a firll dimsion of crystal .im*erry, se F. Seitz,

Z. Krist, 88, 433 (I9S4):.g0, 21jg
(1935); 9r' s6 (1935); 94, 100 (i936); and vol. t-of IntemtiorcI
tobla for'r+ay *rrr;ig;;phv,
5yry9
1*, Birmingham, 1952. A panicuialy redable discsion of sprc grorp-, i, gi'"eo Uy
F. C. Phillips, An inhodrction to agstallographrl, fVil"y, 1963, 3ril
ed-

Crystal Strcture

t\

---^-\.

H
v)

/:

Figure 9a A 6ve-fold axis of srmmen* camot eri5t

in a lattice becaue it is not possible to fill aII space
*-ith a connected arav of pmtagons. In Fig. 32 ue
gire u exmple of re.illa pentagonal packhg *iiicn
cies noi have t.he trulsledonai hvriace of a latdce.

l0 The clvstal lattice is rotated bv a

9 about a lattice point. The vector a b

Figrrre
angle

cffiied into a, by the rctatioo. For special rzlue

of 9 tle rotated lattie mbcids with the orfginal
lattice. For a squ*e lattice tlese special valus
re 9 = |z ud multiplc ttrereof, so that tbe
point group of ttre sqwe lattie includes a
foufold rotation. \!'herever tie rotated lattice

coin_

cides vith the original lattice, the vector a, _

a
vill be a lattice vecto!. Such a lattice vector sill
never be shorter than E becaue there is no lattice
vector shorter than t, except zero. Simila
require

ments determine the special values of

9
possibie lattict

flr al

s.

\--/

I-igure gb Kepier's demonstrahon (Fidntron{

rrundi, 1619) that a seven-fold ads of slTrmei-,
cff1ot eist in a lattice. (Cescttntelte lI'gie. \bt. 6
ilecii. \lunich,

19.1O.)

t3

- 1--i).:,,
:::--ri'::t:<

?_!-

.':

: -.r

.;1

a
Figure

il

ll

Diagrams illustratiag fou

g:""pr: The dots denote

l-iT,
Ient points.
The point group

equiva_

hro no

symmebl- elements, so here

a point
no other point equir.a.lent

hc

to iL For

at

lz

N a minor plane: one

dot on re_
:ner:
trtraoD across ttre minor
plaae becoma
tt,e second doi. Wit-h
a ts.o_fold aris 2,
a rotation of r takes
one dot into ,Jre

otier. \Vith a two_fold axis

ald ooe
minor plaae ttrere is automa6call;.

oa

second

not cornbi'e five-foid point s)-mmetiv qith -.he

required transrational s.!Tnmeh-)..
The arg'"rment aqainst se'en-ford
q'mnetn' is
gi'en
in Fig. gb. The lines of an
^''
algebraic argument are indjcated

i.

e,i".

iif

-{ lattice point group is defined aI the co'ectron

of the s}mmetry
tiore rvhich. u.hen

opera_
anplied abotd a lottice
1:oittf,Iear.e the lattice inrariant.
The possibte
;';;'"i',rTr. ,r" can aiso ha'e mi*6y ys.
'ot"uo*'n",=-il;
flections m about
a plane tluough"a r*tti""
foi.,t. r.rre inversion operation is

r#"# *:

::::"$"1 ;?T::: :" "':#:" in a prane n ormar,i u " .o,uLocatiors of equir.alent

O"J;;"'r;j* n ,o, a* poinr groups in Fig. il.
The symmetrv oP"r"oo::-:l-the
group ;;ry;" point into
al the equivalent
positions. The poinrs themselr.es
nr.ot not'U" tlJ"gfri ;;;;;:il
mebT elements; thev may be
,r*
,d:r: trianglJs-or *i""rf* *[.
elements. The synmetr-y axes
and pl"n", Jf a cube are shown ""'ffi"r'
in Fig. 12.
Ta*Itimercia nal Lattice Tgp es
There is an unlimited number
of possible rattices beca'se there
is no
lenetl's
a
r.ruce transration .,,"",o., o,
",
oo
"i,r'"
*tle
-

fi.l*'Jff:;H
a.n

d b.-A

*.,".J

plane nomal to tle

-minor
u'e have tle
l::
Tu equjvaleDt Point grouD znm
qttt tou
poirts.

2mm

i"Li"tq :' iffil,Lll?;'l H

ffi '?;#X ;

,
invariaat only under rotation
of ri and Zo
lattice poinl
But special lattices'of t]re
^Uo,ri*y
obiique

ti"";

be invariant ,nder rotation

j;li'*!r,;X,-d",*io.."a""u*wemusti-poo.-JJ"u,,"of

""Y,,!;JJ!

'nderone.,;;;;;#Jru[?,"'"T::,:;ffi

":*l#rnilffi :

\@ffijffi
\.

!i-

.')

'.i/7'-

'j.

:..':.1

r
--\

rl
-==-=J
--t ;
,/
'./
.-.-.-.-----r
.//
(e)

id)

(c)

faas of a cube (b) Tbe six diagonal

Parallei to the
a
Figue 1l (a) The t'hree plms of +Tmes)* i"y'tJ*;i;1"
cube' (d) Tbe fou ELad axes of
plme of s\EEetrY - " ""ot'tttt"l'il"t'-*"-;
show
not
is
'it" ,o ii"a *o or " "tut' The ilvesion enter
.i*lt"i

may call
and each leads to what we
there are four distirct types of restriction'

$'pe'^
oblique
types m t'vo dimensiors, the
Thus there are 6ve distinct lattice
for
phrasell
Brrrais^ lattice is the common
lattice and the four qp."JJ*""..
two
in
lattices
Bravais

a special Iattice

there n1s five

a distinct lattice $pe; *" "y that
dimersions'

rl\\e

have not rucceeded

w'hich stuts out "A Bavais

in finding or corotmcting a defrnition
"hm&mental
*'* et"'l* u*""'" The phrre

w";;ilfi';t

lattice is . . ."; the soues

type of lattice" is more zugqestive'

;tyl:t'"t

"

'i 5--

-:,, r]
rI

t5\'

-.+"

/
1 'J

:r"j::_

,::j: a:i_

..1

a..- .
(a)

a
(b)

Square lattice

!ai=ibi; e=e9'

Hexagonal

iaj =

lattie

lbl; c= lme

a
(c) Rctangular lattice
es"
lal* 1lh

(d)

e:

Cntered reciangular tattice;

ax* are sho'm ior both the
primitive ell and for the
rectangular unit cll, for

\rhichiai

Figue

*ib1;P=gO'

13

The point operation 4 requires a square lattice (Fig. 13a). The point
3 and 6 require a hexagonal lattice (Fig. 13b). This Lattice is
invariarrt nnder a rotation 2ri6 about an a:ris throug! a lattice point and rrormal

operations

to the plane.
There are important consequences if the mirror reflection m is preseat.
We write the primitive translation vectors q b in terms of the unit vectors

i, i

along

tle

Cartesian

r, y axes:

t=azi*av9;

b=b"x*b,9.

{4)

If

the primitive vectors are mirrored in &e r axis, then a, b are tuansformed
by the reflection operation into new vectors a', b' giveo by

a'

If

a"*.

ao9 ;

b'=b.k-bui

(5)

the lattiee is invaria-nt under the reflection, t}ten a', b' must be lattice vectors;

that is, tley must be of the form n1a I nzb, rvhere n1 and n2 are integers.

If we take

a=ai;

b=b9;

(6)

then a' - a and b' :

-b, so that the lattice is carried into itseX. The lattice
defined by (6) is rectanguJar (Fig. 13c).

Crystnl Stretwe

. A second distinci possibility for a and b gives another tn;e of lattice

invariant under reflection. Note tl-iat b, rr,ill be a lattice vector if
b':a--b;

(7)

then using (5) rve have

br'=a"-b"=br:

These equations have a soluhon

I

bo'
lf.

a,

A;

ao

bu

= -bu

b,: ]a,; thus a possible

primitive trarxlation vectors for a lattice *'ith mirror sl.rnmetrv

a-ai;

(8)
choice of

is

b=12ai4bui-

(s)

This chorce gives a centered rectangular lattice (Fig. l3d).

We have now exhausted the trvo-dimensional Bravajs lattices u.hich are
consistent *'ith the point-group operai;o;rs appried to lattice points. The
fi,,.e
possibilities in hvo dimensioru are summarized in Table t. rhe point s,-metr,given is that of rhe bttice; an ach:a-l cn'stal siructur. *ay hrrre lor'e. srrrnmeky than its iattice. Thr's it is possible for a crvstal with a sq'are lattice to
have the operation 4 without having all of the operatioru 4mrr.

Table I The ffve tp.o-dimensional latticc trpes

(The notaiion mrn mearls that two mirror lines are preseni)

,{xa of

Conr enhoaal

Lattice

cell

Oblique

Paraleioqram

Square
Hexagooal

Square

Prirnitive lsctr n gulal

Centered rectangular

coventional
celi

a-=b,9-gl'
a-b, p:gO'
a:b, 9: I20'
a=b, 9= 90'
a+b, 9:gO"

60'

rhombus
Rectairgle
Rectarrgle

Point-group srmmetrv of
lattice aboui

latirce poilts
2

lrnm
6mm
2mm

2m

a
Table

The fourteen lattice types in three dimensions

Nmber
of
I

Svstem
I

Resbictiom on

lattices
in

lattie

svstem

srmbols

onventional

samd

ell

mgles

a7b7 c
a* B*t

Triclinic

albt'c
d = y:90'+B

\f snoclinig

P,C

C)rthorhombic

P,C,

Teiragonal

P.

Cubic

Porsc

I,F

I or bcc

a*b* c
a=B=Y=90'

=bt'c
a-B-7=90"

a=b=c
a=B:y=90'

F or fcc
I

a=b=c
a- $- y<I2,0',;.90"

Trigonal

a.: b; c
c=B=9["
T - 120"

HeragonaJ

Th

r ee

-D

imznsional Inui c e

Ty p es

In trvo dimensions the point

gloups are associated rvith five di_fferent

lattices.
In
of
three
dimensions
the point slrnmeu/4 groups requLe the
lrpes
fourteen different (one general arid thjrteen speciaj) lattice types show:a in
Fig. 14 and listed in Table 2. The general lattice t'?e is the h-iclinic lattice.

The fourteen lattice types are conveniently grouped into ,seven systems
sccolding to tle seven types of conventional unit cells: triclinic, monoclinic,
orthorhombic, tetragonal, cubic, higonal, a"d hexagonal. The djvision into
systems is summarized conveniently in terms of tle special axial relatioos for
the conventional unit cells. The axes q b, c and angles a, F, y ue defined in

Fig.

15.

The urrit cells shorvn in Fig. 14 are the eonventional c.ells, and ttrey are
not a-hl,ays primitive cells. Sometimes a nonprimitive cell has a more obvious
connection with the point trynmety elements than has a primitive cell. lVe
now discuss the various lattices by their classification in systerns.

1. In the triclinic system the single lattice $pe has a pfi161iye (P) unit
cell, rvith tluee axes of unequal lengths and unequal angles.

Tetmlonal P

iat:

_-

Monmlinic P

?:rl

-:_-:1.

i_:'_tsj,.'':7if_;+:

Monrclinic C

Triclin

ic

::.-,

Figue 1{ The fourtea Bnrzis or

ue not always the prinitive cells.

space

}afties- The alls shom se the conventional

Figure

15

Crystal ares a,

betrveen b and c.

cells, which

b, c. The ugle a is induded

Table

Charac{eristics of cubic lattices

(Tables of numbers of neighbors and distances in sc, bcc, fec, hcp, and diamond strucfures

are given on pp. 1037-1039 of J. Hirschfelder, C. F.

theorg of gases and. Iiquids, \Vilev, 196{.)
Simple

Cutis, and R. B. Btrd" tr[oleculnr

Bodv<atered

Face<eqtered

\blume, conventiona-l eell

a3

a3

a3

I;ttice

a3

-!-3

\-3

l/62

2i6e

4/az

t)

Sr/2a1,

polnts per ceil

\iolume, prirnitive c.ell
I;ttice poilts per r.nit volume
Numbei of neerest leighbo;s"
Nearest-neighbor distance
\umber of second neighbors
Second neigh'oor dis*ac-e
"

\sst

neighbon

m tle nsst

_ 0.W

a/Zt'z -

tl

la*tice poirts to

dv

givetr

0.7a7a

lattie point.

2. In the monoclirlic svstem there are tr.r'o lattiee qT)es, one uith a primitive unit ceii and the other *ith a nonprimitive conventional cell xfuch may
be base-centered (C) rvilh lattice points at tie centers of tf-ie rectaagular cell
facets

in the c& plane.

3. In ttre orthorhombic svstem ti.ere are four lattice tvpes: one Lattice
has a primitive cell; one lattice is base-centeredl one a bodl'-centered

(I :

German Innen:entrierte); and one is face-center.d (F).

In the tetragonal r-stem the simplest urit is a right square prism; this

-1.

is a primitive cell and is assoclated $-ith a tekagonal space Lattice. A second

tetragonal lattice tlpe is bod1.-centered.
5. In the cubic system there are tl-ree lattices: the simple cubic (sc) lattice,
the body-centered cubic (bcc) lattice, and the face-centered cublc (fcc)
lattice. The characteristics of the three cubic lattices are summarized ia Table 3.
A primitive cell of the body-centered cubic lattice is shown in Fig. 16;
tlre primitive translation vectors are shown in Fig. 17. Trte primitive tmnslation vectors of the face-centered cubic lattice are shown in Fig. 18. The primitive cells contain only one lattice poinl but ttre conventional cubic cells
contain two lattice points (bcc) or four lattice points (fcc).
6. In the trigonal system a rhombohedron is usually chosen as the primitive
cell. The lattice is primitive.
7. In the hexagonal system the converitional cell chosen is a right prism
based on a rhombus rvith an angle of 60'. The lattice is prirnitive. The relaticn
of the rhombic cell with a hexagonal prism is shown in Fig. 19.

aI

I
I

I
I

I
I

I
I

I
I

I
I

Figure 17 Primitive traslation vectors of the bodr <entered

cubic latdce: tiese r.ectors conoect the lattice point at the
origin to latice points at the body.centers. The primiti,,e
cell is obtained on completing tbe rhombohe&on- h tem
of the cube eCge a the prinitil.e .saulation vector ue

^' =

!G+ :. - i);

a,-

s, =.-9,1-i +

+ r)i

c'=--(iij+ir.
Thae primitire

Figure t8 The rhombohedral primitive cell

of tie face-centered
cubic crvstal. The primitive translation vectors
a,, b,, c, conamt
the lattice point at tle origin with lattice
points ,t th" i"". *ot"rr.
As dra*a, the primitive vrctors ae:

a'=;(i+i);
The mgles betrveen

tie

b'-_
ares

it;+i),

t.o *"t.-*gto

of 109"26,

siti

ech otler.

Figure 19 Relation of tie primitive ell

ir. the hexagonal system (heaw lines) to

a prism of
a=b*c.

hexagonal symmetr,v. I{ere

=ft:+ll.

ae 60".

3t

Figue 90 This piaue intercepts ttre a, b, c u6 at 3a, 2b, 2c. The

reciprocals of tiese numbers re !, |, !. The smallat three iltegen
haring tle eme Gtio ue 2, 3, 3, od tbu the \liller ildjces of the
plme ue (233).

(200)

Figure 2l
to (100).

(100)

lr{iiler indices of some important planes in a cubic crystal The plane (200) is paajlel

a
I

I
I

POSITION AND ORIENTAIION OF PI-ANES

IN

CrytUI StrucAtre

CRYSTALS

I
I

I
I

I
I

The position and orientation of a crystal plane are d.etermined

by any
tlree points in the plane, provided the poitrs are not couinear. ff each
of the

points lies on a cn'stal axis, the plane may be qpecified by giving

the positions
of the points along the axes in terms of tie lattice constants. I{ for example,
dte atoms determining the plane have coordinates (4,0,0), (0, I,0), (0,0,2)
relative to the a-xis vectors from some origrn, tle plane may t ,p""in"a
Uy
the three numbers 4, I,2.
But it is more usefi:l for structure analysis to specify the orientation of a
plane by l{iller indices,l2 determined as in Fig. 20:

1. Find the intercepts on the ares a, b, c in terms of the lattice constants.

The ares ma,v*.beprimitive or nonprimitive.
2. Ta&ezdre reciprocals of these numbers and tlien reduce to three integers

.having

the s,rne ralio. usually the smallest tlree integers. The result is en-

closed in pareniheses: (hkl).

For the plane rvhose intercepts a:e 4, I,2 the reciprocals are
], 1, and {
anc ihe rliller indices are (I42). If an intercept is at ininity, the corresponding index is zero. The \liller in&ces of some important planes in a cubic
crvstal are illustrated bv Fig. 2I.
The indices (hkl) ma,v denote a single plane or a set of parallel p1anes.r3
If a plane cuts ari axis on the negative side of the origin, th. *.r-"rporrdirrg
regati'e and is indicated bv placing a minus sign above th" rnde",
T1:t uThe
t/rl1;.
cube faces o[ a cubic cn.sra] are (fOO), fOfOi, (001), (I00),
(010)' a,'.d (001). Pianes equivaient br so:rnmetr.v may be denoted
by curry
bracke's (braces) aro'nd irri]ler i'&ces; tle set of
faces is 1roo1. $e
"ou"
ofien speaL simply of the 100 faces. If rve speal< of the
(200) p1"o" *." *""r,
a plane parallel to (r0o) but cutting the a a-xis at
{a. The formauon of the (rl0),
(111), a-rd (322) planes of an fcc cry-star skucture, starting &om (r00)
planes
of atoms, is showr in Figs. 2la" b, c on p.24.
The indices of a direction in a crystal are expressed as the set
of the
smallest integers which have the ratio of the components of a
vector in the
desired direction referred to the axes. The integers are written
between square
brackets [hkl] . In a cubic crystal t]re r a_ris is the 100] direction;
tn" _ y oi,
t
is the [010] direction. often we spearr of the
[hrcr] and equivarent air""Lo*,
or simply of the [hkl] directions. In cubic crysials the direJtion
[hkr] is arrvays
perpendicular to a plane (hkl) having tie sarne indices (problem
:1, but this
is not generally true in other crystal svstems.
-

their

, .

12

'{ t first sight the uefuLress of the lrriiler indices sems improbable, but cbapter 2 makes
and elegance.

_cmrrnience
l3Other

h, k,

smbols are frequenLlr,

I.

used

creu

bv cn.stallographers; they may ue (, c, o in place of

ou

2la A (110) plare of u fcc cn,sal

*."*.: a built up fron 1I00r ler.en.
":d_S: "":onpmling pbotog:aphs
'T br.J.
ue
F. \icbolas, Atlzs of
^oi"iS65i.oy
crystcJu-7rm. Gordou ud Biqcb,
Figue

2lb .{ (l1l) plane of m fcc cn.stzl

structue, bxed on (100) laven.
Figue

Figure 2lc A (322) plane of m fcc

wsal
structwe, bred on (100) layen. Th"
to_
entration of atoms tends to be lower
in
planes of b.igh indices tban in planes
of low
irdices.

Cryst4l Stflcturc

Figrge 22 Tbe coordnates of the cenh-al

pcilt of a ell ue | ] |, ir terns of the

lengtl of the ues.

POSITION

I\- THE CELL

The positions of a point in a cell is specified in terms of atc,mic clo.dinates

ii7 *'hich each coordinate is a fraction of the axial
l"ngtb, a. b, or c, in
the direction of the coor&nate, u.i.rl'r the origin taken at a corner of a cell. Thus
(Fig. or 1 the coordinaies of tie centra-l point of a cell are i i *. The face_
centered posiHons L'rclude l ] O; O i i; i 0 i. The coordinates of atoms ir fcc
and bcc lattjces are usuall-r giren ia terrns of the conventionai cubic cell.
Tables of crvstal stuchrres usually spec4- the type and size of the cell, a;iri tien
the-v give tle values of the atomic coordinates r,r,
!r,4 for eac! of the atoms
in the cell.

x, g, z

25