10

Metric Tensor and Symmetry

Operations in Crystallography
by
Germano Rigault
This electronic edition may be freely copied and
redistributed for educational or research purposes
only.
It may not be sold for profit nor incorporated in any product sold for profit
without t he express pernfission of The Executive Secretary, International
l,;nion of Crystalk~graphy, 2 Abbey Square, Chest er CIII 211U, I,;K
Co p y r i g h t i n t hi s e l e c t r oni c ectition (i)2001 International [Jnion of
Cr y s t a l l o g r a p h y
Published for the
International Union of Crystallography
by
University College Cardiff Press
Cardiff, Wales
1980 by t he I nt er nat i onal Uni on of Cr ys t al l ogr aphy.
Al l f i ght s r eser ved.
Publ i shed by t he Uni ver si t y Col l ege Car di f f Pr ess f or t he
I nt er nat i onal Uni on of Cr ys t a l l ogr a phy wi t h t he
fi nanci al assi st ance of Une s c o Cont r a c t No. SCf RP 250. 271
Thi s pa mphl e t is one of a seri es pr e pa r e d by t he
Commi ssi on on Cr yst aLl ogr aphi c Te a c hi ng of t he
I nt er nat i onal Uni on of Cr ys t al l ogr aphy, u n d e r t he
Ge ne r a l Edi t or s hi p of Pr of es s or C. A. Tayl or .
Copi es of t hi s pa mphl e t a n d ot he r pa mphl e t s i n
t he seri es ma y be or de r e d di r ect f r om t he
Uni ver si t y Col l ege Car di f f Pr ess,
P. O. Box 78, Car di f f
CF1 1 XL U. K.
I SBN 0 9064-49 14 6
Pr i nt ed in Wal es by Uni ver si t y CoLlege, Cardi ff.
Seri es Pref ace
Th e l ong t e r m ai m of t he Commi s s i on on Cr yst al l ogr aphi c Teachi ng in
est abl i shi ng t hi s p a mp h l e t p r o g r a mme is t o pr oduc e a l ar ge col l ect i on of
shor t s t at ement s each deal i ng wi t h a speci fi c t opi c at a speci fi c l evel . Th e
emphas i s is on a par t i cul ar t eachi ng a ppr oa c h and t her e ma y well, in t i me,
be pa mphl e t s giving al t er nat i ve t eachi ng appr oaches t o t he s a me t opi c. I t
is not t he f unct i on of t he . Commi ssi on t o deci de on t he ' bes t ' appr oach
but t o ma k e all avai l abl e so t hat t eacher s can ma k e t hei r own sel ect i on.
Si mi l arl y, in due cour se, we hope t hat t he s ame t opi cs will be cover ed at
mo r e t han one l evel .
The initial sel ect i on of t en pa mphl e t s publ i s hed t oget her r epr es ent s a
s a mpl e of t he var i ous l evel s and a ppr oa c he s and it is hope d t hat it will
s t i mul at e ma n y mo r e pe opl e t o cont r i but e t o t hi s scheme. I t does not t ake
ver y l ong t o wr i t e a shor t pa mpMe t , but its val ue t o s ome one t eachi ng a
t o p i c f or t he first t i me can be ver y gr eat .
Each pa mphl e t is pr ef aced by a s t a t e me nt of ai ms, l evel , necessar y
backgr ound, et c.
C. A. Ta yl or
Edi t or f or t he Commi s s i on
The financial assistance of UNESCO, ICSU and of the International Union of Crystallog-
raphy in publishing the pamphlets is gratefully acknowledged.
Teaching Aims
To use t he i deas of vect or and mat r i x cal cul us t o i nt r oduce t he concept s
of s ymme t r y oper at i ons and s ymme t r y el ement s and t o der i ve t he cryst al -
l ogr aphi c poi nt gr oups on t hi s basi s.
Level
T h i s is a fai rl y hi gh l evel cour s e whi ch woul d be mos t a ppr opr i a t e t o
t he l at er year s of unde r gr a dua t e st udy or t o t he ear l y year s of pos t -
gr aduat e r esear ch. I t coul d be hel pful in r el at i ng cr yst al l ogr aphy t o ot her
di sci pl i nes such as physi cal chemi st r y and physi cs pr ovi ded t hat t he
ma t he ma t i c a l ba c kgr ound of t he st udent s is hi gh enough.
Background Required
St udent s need a s ound basi c knowl edge of vect or and mat r i x cal cul us
and of gr oup t heor y in or der t o appr eci at e this cour se.
P r a c t i c a l Resources
No par t i cul ar pr act i cal r es our ces ar e r equi r ed.
Time Required for Teaching
Thi s is a me a t y cour se and coul d wel l occupy 7 - 1 0 hour s of t eachi ng
and di scussi on f or full assi mi l at i on.
Metric Tensor and Symmetry Operations
in Crystallography
Ge r ma n o Ri g a u l t
I st i t ut o di Mi ner al ogi a, Uni ver si t ~ di Tor i no, I t al y
I n t r o d u c t i o n
In t he first pa r t of t hi s monogr a ph t he concept s of s ymme t r y ope r a -
t i ons, s ymme t r y el ement s and s ymme t r y gr oups bas ed on t he met r i c
t ens or i nvar i ance ar e i nt r oduced.
In t he s econd par t t he cr yst al l ogr aphi c poi nt gr oups ar e der i ved: first
t he e na nt i omor phi c gr oups usi ng all possi bl e combi nat i ons of t he r ot at i on
axes; secondl y t he c e nt r os ymme t r i c gr oups; and, finally, t he non-
enant i omor phi c, non- c e nt r os ymme t r i c gr oups.
Thi s s cheme is di r ect ed t o st udent s who al r eady have a basi c knowl edge
of vect or and mat r i x cal cul us, and of gr oup t heor y (i.e. st udent s of t he I I I
cour s e in Chemi st r y) .
I hope t hi s pr es ent at i on will be hel pf ul t o t eacher s in r el at i ng s ome
aspect s of cr yst al l ogr aphy t o ot her t opi cs in t he field of physi cal
chemi st r y.
I n a cr yst al l ogr aphy cour s e t hi s subj ect shoul d be pr eceded by an
i nt r oduct i on t o di r ect l at t i ce and t o r eci pr ocal l at t i ce (di st ances and
angl es, t r ans f or mat i ons ) and f ol l owed by a di scussi on of s pace gr oups, i.e.
of t he combi nat i ons of t he possi bl e s ymme t r y oper at i ons of t he t ype
{A/t}.
Metric tensor
The scal ar pr oduc t of t wo vect or s r l and r2 r e f e r r e d t o t he s ame bas e
s ys t em consi st i ng of t he t hr ee non- c opl a na r vect or s "rl, "r2, % is def i ned as:
r l r 2 = ( x i , r I q - y l , r 2 q - z i ' r 3 ) ( x 2 ' r 1 q - y 2 ' r 2 q - z 2 ' r 3 ) . ( 1 )
I n mat r i x not at i on it coul d be wr i t t en:
" ] ? ]
"rl "rl'rl "r2"r~
r l r 2 = - [ X l Y l Z i ] ' r 2 ' ' I ' 1 ~ ' 2 " ~ ' 2 " i ' 2 '1"3 Y2 ; (2)
I..'1" 3 - ,1-1,r 3 ,'1"2,I" 3 ,I" 3 Z 2
i t is easy t o ver i f y t hat f or mul a e (1) and (2) ar e equi val ent . Rel at i on (2)
can be wr i t t en mo r e bri efl y as fol l ows:
r i " r 2 = r'i Gr 2 (3)
I
X2] "
w h e r e r2 i s a c o l u m n m a t r i x Y2 a n d r~ a t r a n s p o s e d c o l u mn ma t r i x
. Z2
[ x l y l z~]; 9 i s t h e 3 x 3 m a t r i x o f r e l a t i o n ( 2) a n d i s c a l l e d a m e t r i c m a t r i x
o r me t r i c t e n s o r * , b e c a u s e i t s e l e m e n t s g~i =' r ~ 'r~ a r e d e p e n d e n t b o t h o n
t h e l e n g t h o f t h e b a s e v e c t o r s a n d o n t h e a n g l e s f o r m e d b y t h e m .
I f i n (3) we a s s u me r l = r2, w e h a v e :
r ~ - r ~ = [ r ~ l " I h [ = 6Gr~ ( 4 )
a n d t h e r e f o r e :
I r l l = ( 5 )
O n t h e o t h e r h a n d , b e a r i n g i n m i n d t h a t r l r2 = [rll Ir21 c o s ~b, w h e r e ~fi
i s t h e a n g l e b e t w e e n r l a n d r2, we h a v e :
h " r2 = I r J Ir2[ c o s ~ = r ] G r 2 ( 6)
a n d f i na l l y, u s i n g r e l a t i o n ( 5) , we o b t a i n :
r'~ Gr 2
c o s ( 7 )
E q u a t i o n s (5) a n d (7) a r e t h e r u l e s t o o b t a i n t h e v e c t o r l e n g t h s a n d t h e
a n g l e s b e t w e e n v e c t o r s . T h e s p a c e i n wh i c h t h e l e n g t h s a n d t h e a n g l e s
b e t w e e n v e c t o r s a r e d e f i n e d , i s c a l l e d me t r i c s p a c e . T h e me t r i c i s g i v e n b y
t h e G ma t r i x .
S y m m e t r y o p e r a t i o n s
W e c a n r e p r e s e n t e v e r y s y m m e t r y o p e r a t i o n b y a m a t r i x A :
[ a l l a 1 2 a 1 3 ]
A = | a 2 , . a22 o 2 3 / ; ( 8 )
La31 a32 a33..I
t h e v a l u e o f t h e e l e m e n t s o f t h i s ma t r i x i s d e p e n d e n t o n t h e k i n d a n d
o r i e n t a t i o n o f t h e c o r r e s p o n d i n g s y m m e t r y e l e m e n t wi t h r e s p e c t t o t h e
b a s e s y s t e m, a n d o n t h e c h o i c e o f t h e l a t t e r . I n f a c t , i n d i r e c t s p a c e a
s y m m e t r y o p e r a t i o n t r a n s f o r m s a g i v e n v e c t o r r i n t o t h e v e c t o r r ' ; i n
m a t r i x n o t a t i o n we c a n wr i t e :
r ' : A r ( 9)
w h e r e r a n d r ' a r e t h e t wo c o l u mn ma t r i c e s w h o s e e l e m e n t s a r e g i v e n b y
t h e c o m p o n e n t s o f t h e t wo v e c t o r s .
Note that on the basis of the commutative property of the scalar product the G matrix is
symmetric.
2
I f t h e bas e s ys t e m is gi ven by t he t h r e e ve c t or s ~1, 'r2, ~3 of a pr i mi t i ve
l at t i ce, t h e e l e me nt s % of t he A ma t r i x ar e neces s ar i l y i nt eger s. I n f act
r e l a t i on (9) mu s t hol d t r ue f o r e ve r y v e c t o r r of t he l at t i ce; A t r a ns f or ms r
i n a n o t h e r v e c t o r r ' : in t hi s case t he c o mp o n e n t s of r a nd r ' ar e i nt eger s,
a nd s i nce r e l a t i on (9) hol ds f o r e ve r y g r o u p of t h r e e i nt eger s r el at i ve t o r,
t h e e l e me n t s of A mu s t b e i nt eger s .
We will n o w e x a mi n e o t h e r r es t r i ct i ons on A whi ch al l ow us t o def i ne
t h e si ngl e e l e me nt s % as a f unc t i on of t he me t r i c t ens or . A s y mme t r y
o p e r a t i o n obvi ous l y mu s t not c h a n g e t he l engt h of a v e c t o r or t he angl e
b e t we e n vect or s . Th e r e f o r e we ha ve :
r ' r ' = r r
f r o m whi ch f oUows, a ppl yi ng r e l a t i on (4):
r " ar ' = r ' Gr
a n d f r o m (9):
r ' A ' GAr = r ' Gr
a n d fi nal l y, s i nce t he p r e v i o u s r el at i on mu s t hol d f o r a ny va l ue of r :
G = A' GA (10)
i . e. :
g,2 g o _ = g 2 3 ] = | a l = a = = a 3 o - l l g , . _ a = 2 a 2 3 |
gz3 g23 g33 I_a13 ao_3 a33--ILgz3 go_3 g33JLa31 a32 a33-1
(11)
Thi s i dent i t y is t he mat r i x e xpr e s s i on of t he s cal ar p r o d u c t c ons e r va t i on
on t he c r ys t a l l ogr a phi c ba s e s ys t em. Al l t he ma t r i c e s sat i sf yi ng r el at i on
(10), ar e s y mme t r y o p e r a t i o n s on t he ba s e s ys t e m def i ned by G (see t he
e x a mp l e i n t he Ap p e n d i x ) .
F r o m r el at i on (10), us i ng mat r i x a nd d e t e r mi n a n t pr oper t i es , we o b -
t ai n:
I GI = I A' I " I GI " I AI
f r o m whi ch, k e e p i n g i n mi n d t ha t I A ' l = I A [ , f ol l ows t ha t t he d e t e r mi n a n t
as s oci at ed wi t h t he A mat r i x mu s t b e equal t o +1 . I f t he d e t e r mi n a n t is
e qua l t o +1 t he s y mme t r y o p e r a t i o n is s ai d t o b e l o n g t o t he t ype I and it
is def i ned as a r ot a t i on; if t he d e t e r mi n a n t is equal t o - 1 t he s y mme t r y
o p e r a t i o n is of t y p e I I and def i ned as a r o t o i n v e r s i o n Y
* One can demonstrate in fact that, since the determinant of A is equal to +l , there is no
variation of the unit-ceU volume; when the value of the determinant is negative the base
system passes from a fight-handed one to a left-handed one and vice versa.
Symmetry elements and their orientation
Th e s y mme t r y e l e me n t is t he g e o me t r i c e nt i t y a r o u n d whi ch o n e o r
mo r e s y mme t r y o p e r a t i o n s t a k e pl ace, a nd c o r r e s p o n d s t o t he l ocus of t he
poi nt s t ha t ar e l eft u n mo v e d by t hes e ope r a t i ons . Th e pos i t i on of t he
s y mme t r y e l e me n t is o b t a i n e d by s ol vi ng t he e q u a t i o n :
Ar = r
f r o m whi ch
( A- 1 ) r = 0
wh e r e i is t he uni t mat r i x. A s ol ut i on, o t h e r t ha n t he t ri vi al s ol ut i on r = 0,
can be o b t a i n e d onl y if t he c ondi t i on I A- 11 = 0 is sat i sfi ed. I f t hi s doe s
n o t h a p p e n , it is ne c e s s a r y t o t a ke i nt o a c c o u n t t he mat r i x A A.
Rotati ons compatible with a lattice base system
I f mat r i x A r e pr e s e nt s a t ype I s y mme t r y ope r a t i on, we can cal cul at e
t h e r ot a t i on angl e a f r o m t he va l ue of t he A ma t r i x t r ace. We mus t
r e me mb e r t ha t t he t r a c e of A is i nva f i a nt wi t h r e s pe c t t o a bas e s ys t e m
t r a ns f or ma t i on.
I n a l at t i ce ba s e s ys t e m t he t r a c e is an i nt e ge r n u mb e r , s i nce t he
e l e me nt s of t he ma t r i x ar e i nt eger s . I n an o r t h 0 n o r ma l ba s e s ys t em, t he
c ount e r - c l oc kwi s e r ot a t i on of an angl e a, f o r e xa mpl e , a r o u n d t he z axi s
is gi ven by:
si n a cos ~
0 0
a n d t he n t he t r a c e is equal t o 2 cos o~ + 1.
We ha ve t hen: 2 cos a + 1 = an i nt eger , f r o m whi ch it is s een t ha t t he
val ues of o~ c o mp a t i b l e wi t h a l at t i ce bas e s ys t e m ar e: 60 , 90 , 120 ,
180 , 240 , 270 , 300 , 360 .
Symmetry groups
I f A1 a nd A2 ar e t wo ma t r i c e s r e pr e s e nt i ng a s y mme t r y ope r a t i on, it is
n o t di ffi cul t t o d e mo n s t r a t e t ha t t he p r o d u c t mat r i x A = AI " Az al so
r e pr e s e nt s a s y mme t r y ope r a t i on. I n f act , s i nce A~GAI =G a nd
A t2GA2 = G we ha ve :
( Az " A2) t G ( A1 " A2) = A~A~ G A I A 2 = A~GA2 = G.
Thi s r es ul t obvi ous l y hol ds n o t onl y f or t he p r o d u c t of t wo ma t r i c e s
A1 A2, b u t al so f o r t he p r o d u c t of s ever al ma t r i c e s A~ A2 A3 (a
speci al case of t hi s is AT).
Fu r t h e r mo r e , if A1 r e p r e s e n t s a s y mme t r y o p e r a t i o n , A? t al so doe s : in
f act f r o m r e l a t i on A~ G A~ = G, p r e - a nd pos t - mul t i pl yi ng b o t h me m-
be r s by (A~) -1 a n d by (A~) -~ r es pect i vel y, a nd k e e p i n g i n mi n d t ha t
( A~) - 1 = ( ATe) ' we obt a i n:
G= ( A?~) ' G- (A~-~).
4
Fi nal l y it is obvi ous t hat mat r i x 1 r epr es ent s a s ymme t r y oper at i on
(i dent i t y) no ma t t e r what t he bas e s ys t em def i ned by G ma y be. In t hi s
way we have de mons t r a t e d t hat all gr oup t heor y post ul at es ar e appl i cabl e
t o t he s ymme t r y oper at i ons . The r e f or e t he s ymme t r y oper at i ons ar e t he
e l e me nt s of a gr oup, cal l ed a s y mme t r y gr oup. Si nce all s ymme t r y
oper at i ons At l eave a poi nt wi t h coor di nat es (0, 0, 0,) unchanged, (i.e. all
t he s ymme t r y el ement s pass t hr ough t hat poi nt ) t hese s ymme t r y gr oups
ar e cal l ed poi nt gr oups.
De r i vat i on of t he Crys t al l ographi c Po i nt Gr oups
Groups containing only one rotation axis
I f A1 r epr es ent s a r ot at i on of an angl e a ar ound a gi ven axis, A~,
A~ . . . . . A~ = 1 ar e t he s ymme t r y oper at i ons cor r es pondi ng t o r ot at i ons of
2a. , 3 a . . . . . n a = 360 r espect i vel y, ar ound t he s ame axis; keepi ng in
mi nd t he val ues of a compat i bl e wi t h a l at t i ce bas e s ys t em we obt ai n t he
gr oups n a me d by t he s ymbol n, i.e. 1, 2, 3, 4, 6.
Groups containing more than one rotation axis
Let us t ake t wo s ymme t r y oper at i ons : t he first one cor r es pondi ng t o a
r ot at i on of an angl e a ar ound one axis, and t he second one t o a r ot at i on
of an angl e /3 ar ound a not he r axis. Le t us call o) t he angl e bet ween t he
t wo axes. Then, t he pr oduct of t he t wo r ot at i on mat r i ces is also a r ot at i on
mat r i x. The r ot at i on axis of t he pr oduc t mat r i x is, in gener al , or i ent ed in a
di f f er ent way t han t he ot her t wo. We can obt ai n t he mat r i ces cor r es pond-
i ng t o s ymme t r y oper at i ons in t he f ol l owi ng ma nne r : f or a gi ven or t ho-
nor mal vect or basi s, A 1 A 2 A 3 (Fig. 1), t he s ymme t r y oper at i on cor r es-
pondi ng t o a count er - cl ockwi s e r ot at i on of an angl e a ar ound t he A3 axis
is r e pr e s e nt e d by t he mat r i x:
A3
A' 3
A2
Fig. 1.
R 3 - [ s i 0 o c o s o 0
5
If, on t he ot her hand, t he r ot at i on t akes pl ace ar ound t he A~ axis,
whi ch lies on t he pl ane det er mi ned by A1 and As and f or ms t he angl e ~o
wi t h As (Fig. 1), t he cor r espondi ng s ymmet r y oper at i on is gi ven by:
wher e:
R 3 , = R 2 R s R21
[ c 0 s i ; ]
Rz = 1
L- s i n co 0 cos~0_J
r epr esent s a count er - cl ockwi se r ot at i on of an angl e w ar ound A2. We
have t o bear in mi nd, in fact , t hat R2 R3 t {21 r epr esent s t he s ymmet r y
oper at i on Rs as it is t r ans f or med by t he oper at i on Rz.
In explicit f or m we have:
[ COCO 0 s i ; c o ] [ c o s a L 0 - s i n a ! ] [ Co O) 0 - s O~o l
L- - s i n co 0 COS WJ 0 Lsi n co 0 COS Co J
cos2 w cos a +si n2 o) - c o s ~o sin a --cos ~o sin ~o cos a + sin ~o cos col
= sin a cos ~o cos o~ - s i n a sin co .
- s i n ~o cos ~o cos ~ + cos ~o sin ~0 sin ~o sin a sin 2 co cos a + cos z ~o
The count er - cl ockwi se r ot at i on of an angl e /3 ar ound t he A3 axis is
gi ven by t he mat ri x:
! ]
c o s 0
The combi nat i on of t wo r ot at i ons ( one of an angl e /3 ar ound t he A 3
axis and t he ot her one of an angl e a ar ound t he A3, axis whi ch f or ms an
angl e co wi t h A3 and lies on t he pl ane A1A3) is also a r ot at i on,
r epr es ent ed by t he R mat ri x, given by:
R = R3, R3.
[ c o s 2 mc o s a +s i n 2 ~o - c o s ws i n a - c o s co sin o) cos a + sin ~o cos w]
sin a cos co cos a - s i n a sin co .
- s i n co cos ~0 cos a + cos co sin w sin w sin a sin 2 ~o cos a + cos z w
[ ' cos 13 - s i n / 3 i l
. [ s i ; / 3 cos/30 "
T h e t r a c e of t h e R ma t r i x , gi ve n b y t h e s u m of t h e e l e me n t s of t h e
p r i n c i p a l d i a g o n a l , i s:
cos 2 09 c os ~x c os / 3 + si n 2 09 c os / 3 - cos 09 si n c~ s i n/ 3 - - -
- - - s i n cz c os 09 s i n / 3 + c o s a c os / 3
- - - - si n ~ 09 c os o~ + c o s 2 09
i . e o
t r a c e = cos 2 09 ( cos o~ c os / 3 + 1) + si n' - 09 ( cos / 3 + c os a )
- 2 c os 09 (si n o~ s i n/ 3) + c os ~ c os / 3
= c os 2 09(cos ~ c os / 3 - c o s o~ - c o s / 3 + 1)
- 2 c o s 09 si n o~ s i n / 3 + c o s oL c os / 3 + c o s ~ + c o s / 3 . ( 12)
Th i s r o t a t i o n R mu s t b e c o mp a t i b l e wi t h t h e l a t t i c e as wel l . T h e r e f o r e ,
t h e v a l u e of t h e t r a c e , i n v a r i a n t wi t h r e s p e c t t o a b a s e s y s t e m t r a n s f o r ma -
t i on, mu s t b e an i n t e g e r . T h e p o s s i b l e v a l u e s of t h e t r a c e a r e : + 3, + 2,
+ 1, 0, - 1. Th e s e n u mb e r s gi ve t h e o r d e r of t h e r e s u l t i n g r o t a t i o n axi s.
Wh e n we as s i gn t o o~ a n d /3 i n t h e e x p r e s s i o n ( 12) al l t h e p o s s i b l e
v a l u e s , d e p e n d i n g u p o n t h e o r d e r of t h e r o t a t i o n axi s, we o b t a i n t h e
s e c o n d d e g r e e e q u a t i o n s i n cos 09 l i s t e d i n T a b l e 1, wh e r e m i s an i n t e g e r
r e p r e s e n t i n g t h e t r a c e of t h e R ma t r i x .
I n T a b l e 1 t h o s e s o l u t i o n s f or wh i c h c os co i s g r e a t e r t h a n 1 a r e
o b v i o u s l y n o t s h o wn , as we l l as t h o s e t h a t d o n o t ~ v e as a r e s u l t b o t h co
a n d 1 8 0 - o 9 . Th i s l a s t c o n d i t i o n i s e v i d e n t l y n e c e s s a r y i f t wo a xe s
i n t e r s e c t .
On t h e ba s i s of t h e r e s u l t s l i s t e d i n t h e t a b l e , we c a n o b t a i n t h e axi s
c o mb i n a t i o n s s h o wn i n Fi g. 2, i . e. t h e p o i n t g r o u p s 222, 32, 422, 622, 23,
4 3 2 .
Gr o u p s c o n t 2 i n i n g t y p e I I s y mme t r y o p e r a t i o n s
T o d e r i v e t h e p o i n t g r o u p s wh i c h c o n t a i n t y p e I I s y mme t r y o p e r a t i o n s
as we l l , i t i s n e c e s s a r y t o r e me mb e r t h a t t h e p r o d u c t of t wo o p e r a t i o n s of
t h e s a me t y p e i s an o p e r a t i o n of t y p e I , wh i l e t h e p r o d u c t of t wo
o p e r a t i o n s of d i f f e r e n t t y p e i s an o p e r a t i o n of t y p e I I .
I n s uch p o i n t g r o u p s t h e o p e r a t i o n s of t y p e I , e q u a l i n n u mb e r t o t h o s e
of t y p e I I , f o r m a g r o u p .
F r o m t h e 11 g r o u p s gi ve n a b o v e we c a n o b t a i n 11 o t h e r p o i n t g r o u p s
wh i c h h a v e as e l e me n t s t h e t y p e I o p e r a t i o n s , p l u s o t h e r o p e r a t i o n s
o b t a i n e d f r o m t h e s e b y c o mb i n i n g t h e m wi t h t h e i n v e r s i o n o p e r a t i o n ,
Table I
O r d e r
O r d e r o f t h e
o f t h e r e s u l t a n t
a x e s ~ T r a c e m P o s s i b l e v a l u e s o f co a x i s
O r i e n t a t i o n 2
+ 3 0 , 1 8 0 1 - -
+ 2 3 0 , 1 5 0 , 2 1 0 , 3 3 0 6 0 1 0
2 - 2 . 4 c o s 2 ~ o - l - m= 0 + 1 4 5 , 1 3 5 , 2 2 5 , 3 1 5 4 0 1 0
0 6 0 , 1 2 0 , 2 4 0 , 3 0 0 3 0 1 0
- 1 9 0 , 2 7 0 2 0 1 0
+ 2 0 , 1 8 0 6 0 0 1
+ 1 3 5 1 6 ' , 1 4 4 4 4 ' , 4
3 - 2 3 c o s : oJ - 1 - m = 0 2 1 5 1 6 " 3 2 4 4 4 '
0 5 4 4 4 ' , 1 2 5 1 6 ' , 3
2 3 4 4 4 ' , 3 0 5 o 1 6 '
- I 9 0 , 2 7 0 2 112 - - f ~ 2 0
+ 1 0 , 1 8 0 4 0 0 1
' ~ o o
4 - 2 _ c o s - co - 1 - m = 0 0 4 5 , 1 3 5 , 2 2 5 , 3 1 5 3 1 / , / 3 - 1 / , / 3 1 / , 7 3
- 1 9 0 , 2 7 0 2 1 / , ~ - - 1 / , ~ 0
0 0 , 1 8 0 3 0 0 1
6 - 2 c os ' - co - 1 - m = 0 - 1 9 0 , 2 7 0 2 , f 3 / 2 - 1 / 2 0
3 - 3 9 c o s " - ~ - 6 c o s ~ 0 + 3 1 8 0 1 - -
0 0 , 1 0 9 o 2 8 ' , 2 5 0 0 3 2 ' 3 0 0 1
- 3 - 4 m= 0 - 1 7 0 o 3 2 ' , 2 8 9 0 2 8 ' 2
4 - 3 3 c os ' - ~ o - 2 , / 3 c o s ro + 1 1 2 5 0 1 6 ' , 2 3 4 0 4 4 ' 4
- 1 - 2 m= 0 - 1 5 4 4 4 ' , 3 0 5 0 1 6 ' 2
6 - 3 3 c os ' - m - 6 c o s ~o + 2 1 8 0 6 0 0 1
- 1 - 4 m= 0 - 1 0 2 0 0 1
4 - 4 cos"- ~ - 2 c o s co + 3 1 8 0 1 - -
0 9 0 , 2 7 0 3 1 / , f 3 - 1 / , f i 1/,f3~
- m = 0 - i 0 2 0 0 1
6 - 4 c o s 2 co - 2wz'3 c o s co t h e r e a r e n o
+ 1 - 2 m = 0 p o s s i b l e s o l u t i o n s
6 - 6 c o s ' - ~o - 6 c o s co + 3 1 8 0 1 - -
+ 5 - 4 m= 0 0 0 3 0 0 1
1 T h e f i r s t r o t a t i o n a x i s i s c o i n c i d e n t w i t h A 3 , t h e s e c o n d o n e w i t h A y .
2 T h e r e s u l t i n g a x i s o r i e n t a t i o n i s N v e n b y t h e d i r e c t i o n c o s i n e s r e f e r r e d t o t h e o r t h o n o r ma l b a s e s y s t e m
AI A2A 3 a n d i t i s o b t a i n e d s o l v i n g t h e e q u a t i o n ( R - 1 ) x = 0.
r e pr e s e nt e d by t he mat r i x:
i .
0
Th e c e nt r os ymme t r i c gr oups so obt ai ned, whi ch ha ve an or de r doubl e
with. r es pect t o t h e or de r of t he gr oups wi t h whi ch we st ar t ed, ar e
8
Q
T
222 32
- ;
422 622
" / ~ , ~ ~
23 432
Fig. 2.
Table 2
Or d e r
24
12
8
6
4
3
2
1
432
l
23
222
422
4
1
622
6 32
r espect i vel y:
-1, 2 / m, -3, 4 / m, 6 / m, mmm, 3ra, 4 / mmm, 6 / mmm, m3, m3 m.
I t is al so possi bl e t o obt ai n gr oups cont ai ni ng t ype I I s ymme t r y oper at i ons
but whi ch do not cont ai n t he i nver si on oper at i on. In t hi s case we mus t first
obt ai n, f r om t he st ar t i ng gr oups whi ch cont ai n onl y t ype I s ymme t r y
oper at i ons , t he cor r es pondi ng s ubgr oups , whi ch ha ve or der wi t h r es pect
t o t he st ar t i ng gr oups.
Fr om t he s cheme shown in Ta bl e 2 we see t hat t her e ar e 10 s ubgr oups
sat i sfyi ng t hi s condi t i on. So, t o obt ai n t he new gr oups we mul t i pl y by t he
i nver si on oper at i on all t he oper at i ons of t he st ar t i ng gr oup whi ch do not
bel ong t o t he s ubgr oup.
The s um of t he oper at i ons obt ai ned in t hi s way, pl us t he oper at i ons
bel ongi ng t o t he s ubgr oup gi ves all t he el ement s of t he new gr oup. Th e or de r
of t he new gr oup is t hen equal t o t he or der of t he st ar t i ng gr oup.
Let us fully anal yse an exampl e: t he gr oup 422, of or der 8, has t he gr oups 4
and 222 as s ubgr oups of or de r 4.
In t he first case, t he s ubgr oup 4 cont ai ns t he symmet r Y oper at i ons 41, 42, 4 3 ,
1; t her ef or e t he oper at i ons cor r es pondi ng t o an 180 r ot at i on ar ound t he axis
or t hogonal t o t he 4- f ol d axis ar e i nver t ed. In t hi s way we obt ai n mi r r or pl anes
par al l el t o t he 4- f ol d axis, and t he r esul t i ng poi nt gr oup is 4r am.
In t he s econd case, t he s ubgr oup 222 cont ai ns t hr ee 180 r ot at i ons ar ound
t hr ee per pendi cul ar axes. Th e oper at i ons i nver t ed in t hi s case ar e 41, 43 , 21 lo,
21 ~0- We obt ai n t he oper at i ons : ~1, ~3, mtlo0~ ' m(1 r0}; t he r es ul t i ngpoi nt gr oup
is Z~2m. Al t oge t he r we can der i ve 10 gr oups, usi ng t he f ol l owi ng scheme. ( The
10
s u b g r o u p ut i l i zed is s hown i n pa r e nt he s e s . ) -
4 3 2 - (23) ~ 4-3m
6 2 2 - (6) ~ 6ram
6 2 2 - (32) > 6 m2
4 2 2 - (4) > 4 r a m
4 2 2 - ( 222) > 42r n
6 - (3) ~
3 2 - (3) > 3 m
4 - - (2) :, 4
2 2 2 - (2) > ram2
2 - - (1) , m
Al t o g e t h e r t hi r t y t wo p o i n t g r o u p s ar e pos s i bl e i n t h r e e - d i me n s i o n a l s pa c e :
11 e n a n t i o mo r p h i c ; 11 c e n t r o s y mme t r i c ; a nd 10 n o n - e n a n t i o mo r p h i c ,
n o n - c e n t r o s y mme t r i c .
Ap p e n d i x
Le t us e xa mi ne , as an e xa mpl e , t he cubi c l at t i ce: s i nce t he uni t cell
c ons t a nt s ar e a0 = bo = Co, oe =/ 3 = 3 ' = 90 , t he me t r i c t e n s o r G is gi ven
by:
G=
F r o m r el at i on (10) we ha ve :
?000]
g t l
0 g n
gl l " 1 = g n " A' 1 A
a n d c o n s e q u e n t l y :
A' ' A=I .
I n t hi s pa r t i c ul a r case t h e ma t r i c e s A ar e s uch t ha t t hei r i nver s e A - 1 is
e qua l t o t hei r t r a n s p o s e d ma t r i x A' ; t h e r e f o r e we can obt a i n t he f ol l ow-
i ng r el at i ons :
a~an + azla21 + a3~a3~ = 1 (11)
alia12+ a 2 1 a 2 2 + a31a32 = 0 (12)
aal a 1 3 + a21 a2z + a3a a33 = 0 ( 1 3 )
alza12 + a22a22 + a32a32 = 1 (22)
a12a13 + a22a23 + a32a33-- 0 (23)
aa3a13 + aEaa2a + aaaa33 = 1. (33)
Re l a t i o n s (11), (22), (33) i mp o s e t he c ondi t i on t hat , in e a c h c o l u mn of t he
11
A matrix, one element is equal to 1, and the ot her two are equal to
zero. Relations (12), (13), (23) impose the same condition for each row,
since the element different from zero of each column must lie in a
different row from the one occupied by the non-zero element of the ot her
two columns.
In conclusion the symmet ry operations compatible with a cubic lattice
are represent ed by the following matrices:
[ i ! l [ i i l I i l ! l
1 , 0 , 0 ,
0 1 0
I ! i ] 0 [ i i l 0 I ! i l 0
plus those obt ai ned from the above matrices, considering, for each of
them, all the possible permut at i ons of one, two and three negative signs.
It is not difficult to see that from each of the above six matrices, we can
obtain seven others containing negative elements. The symmet ry opera-
tions compatible with a cubic lattice are, thus, 48 in all. Thei r respective
matrices are shown in Table 3. For each matrix in the table the corres-
pondi ng symmet ry operation and the orientation of the symmet ry ele-
ment, derived as above, are given.
From the table it is seen that the symmet ry operation correspondi ng to
a rotation of 60 , i.e. symmet ry element of order 6, is incompatible with
the cubic lattice, but is compatible with a different lattice (ao = bo, Co,
a =/3 = 90 , , / = 120). As it is known, all 32 point groups are subg-roups
of m3m or 6/mrnm or both.
Finally, the relation A' GA = G can be used to derive, if matrix A is
known, the metric tensor compatible with the symmet ry operation A.
12
Table 3. A matrices for the cubic lattice
li!] o, [iI ~o o~ [i!] o ' I' oo o~ir [i ] o~ ~o [, oo o~i] Ifi)o , I!il o
z T m ( ~ o o ) m ( o ~ o ) m ( o o ~ ) 2 [ , o o ] 2 [ 0 , 0 ] 2 1 o o i ]
[i!] o, liiJ ~ li o , iJ [il o , o, li ~o il [!I o il
I
411oo] 4[ 0; {0] 4[ oi o] 4roox] 4[oo,]
--I ----I - - I ----I --I ----I
4 [ ~ o o ] 4[~oo] 4[o:~o] 4[oxo] 4[oo:q 4 [ o o ~ ]
[iiJ o, [i,il o [!iI o ~ li~ii o I!!] ~ [i ~ ] oo o~ [il o~ ~o li~!l o
[!o ~ i] [o~ ~o oo !] [i ~ i] [!,oj oo o~ [oo ~o o~ i] {i ~ o !] [i oo o~ ~o l [ ~o oo o,o o,]
- I --I ----I - I - - - I - - I - - - I
3 E , , , ] ~ [ ~ , , ] 3 ~ , , ] 3 ~ , , ] 3 ~ T , ] s ~ , j 3 [ , ~ , ] 3 [ , ~ ]
I ! o , o , o j [ o o i ] o~ ~o [ ! ' i ] o [ i : ! ] ~ [ i i ~o ~ { ! ~ i ] o o
2 [ o H ] 2 D o I ] 2 [ x x o ] 2 [ o i x ] e [ T o x ] 2 [ i i o ]
[ i ] ~ o o ~ { i o , ) j [ o ~ o o ~ o i l [ i i ] o , [ i o , i l [ i ' i ] o
13
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