Appendix 1

CHARACTER TABLES

The character tables for the more common point groups are presented.
The last two columns of each character table list the infrared and Raman
activity of the particular species. If one or more of the components of the
polarizability a xx , a xy ' etc., is listed in the row for a certain species in
the last column, that species is Raman active. Similarly, if one or more
of the translation components Tz, T y , and Tz is listed in the next-to-last
column, the species is infrared active. The components of the change in the
dipole moment (/hz, /hy' /hz) should be listed in this column as wen as the
components of translation (Tz, Ty , Tz). However, to save space, since
they always occur together (both are vectors and transform in the same
way if the symmetry operation is carried out similarly), the former are
omitted in the character tables in this appendix. Also listed in the next-to-
last column are the components for the rotational coordinates R z ' R y ,
R z • The subscripts x, y, z indicate the direction in which the translation or
dipole moment change occurs for a particular vibrational species. When
the components of translation, change in dipole moment, or polarizability
are degenerate, they are enclosed in parentheses.

1. Tbe C s , Ci' and Cn Groups

Activity
C. E (J",y
IR Raman

A' 1 1 T"" Ty , R z axx , Ct.V1J , a zz , Ct.a;1I

A" 1 -1 Tz, R"" R y Ct.1IZ , a xz

201
202 Appendix 1

Activity
Ci E i
IR Raman

Ag 1 1 R x , R y , R. eta;x, ety'Y' et zz

A" 1 -1 T x , T., T.

Activity
C. E C'•
IR Raman

A 1 1 T., R. etxa:, (ty'Y , Ctzz , ctx'Y

B 1 -1 Tx , T., R x , R. a yZ ' Ctcvz

Activity
C3 E C3 C'3
IR Raman

A 1 1 1 Tz, R z ct xx + l:t yy , l:tzz

E
{~ :*} :*} (Tx , Ty)
(R x , R y)
(a xx - ayy , a XY )' (a xz , a yz)

e = e21'li/3,

Activity
C. E C. C. C34
IR Raman

A 1 1 1 1 Tz, R z ct xx + (lyy, l:tzz

B 1 -1 1 -1 ct xx - (lyy, (txy

E
{~
i
-i
-1
-1 -:} (Tx , Ty)(R x , R y) (a xz , Ci yz )
Character Tables 203

Activity
Cs E Cs C's C'S C'5
IR Raman
--
A 1 1 1 1 1 Tz, R z a xx + fX yU ' CXzz

EI
{~
S

s*
s'
c: 2 *
s'*
s' :*} (Tx , Ty)(R x , R y) (a xz , a yz)

s' s* s
E.
{~ c: 2 * 0 e*
s'*}
o'
(a xx - a yy , a XY )

Activity
C. C' cs5
E C. C. C. • IR Raman

A 1 1 1 1 1 1 Tz, R z (Xxx + fX yy , CXzz

B 1 -1 1 -1 1 -1

EI
{~
0
0*
-0*
-0
-1
-1
-0
-0* :*} (Tx , Ty)(R x , R y) (a xz , a yz )

1
{~
-0* -0 -0*
-0 } (a xx - a yy , a XY )
E.
-0 -0* 1 -0 -0*

e = e 2Jti / 6 .

2. The Cnv Groups

Activity
c.v E C. G,,(xz) G.(yz)
IR Raman
-
Al 1 1 1 1 Tz lXxx, fX lIy , cxzz
A. 1 1 -1 -1 Rz a",y
BI 1 -1 1 -1 T"" R y a",z
B. 1 -1 -1 1 Ty , R", a vz
204 Appendix 1

Activity
C s• E 2Cs 3eT.
IR Raman

Al 1 1 1 T. axa: + ay'U, a zz

Az 1 1 -1 R.
E 2 -1 0 (T", T y), (R", R y) (a=-a w , a xv )' (ay., a",.)

Activity
C 4V E 2q C'
• 2eT. 2eTa
IR Raman

Al 1 1 1 1 1 T. a= + ay., a••
Az 1 1 1 -1 -1 R.
BI 1 -1 1 1 -1 a:tZ - a VlI
B. 1 -1 1 -1 1 a xv
E 2 0 -2 0 0 (T", T y), (R", R.) (ay., a".)

Activity
Cs• E 2Cs 2q SeT.
IR Raman

Al 1 1 1 1 T. aa:z +a llll , an

A. 1 1 1 -1 R.
EI 2 2 cos 72° 2 cos 144° 0 (T", T.), (R", R y ) (a"., a•• )
E. 2 2 cos 144° 2 cos 72° 0 (a"" - a •• , a",.)

Activity
C,. E 2C, 2C. C. 3eT. 3eTa
IR Raman

Al 1 1 1 1 1 1 T. a:vx + a ll'll' azz

A. 1 1 1 1 -1 -1 R.
BI 1 -1 1 -1 1 -1
B. 1 -1 1 -1 -1 1
EI 2 1 -1 -2 0 0 (T", T.), (R", R.) (a"., a •• )
E. 2 -1 -1 2 0 0 (a"" - a •• ), (axv)
Character Tables 205

3. The Cnh Groups

Activity
c_h E c_ i Gh

IR Raman

Ag 1 1 1 1 R. (Xxx, (XlIY , U zz , (XXY

A" 1 1 -1 -1 T.
Bg 1 -1 1 -1 R x , R. a yZ ' a xz
Bu 1 -1 -1 1 Tx , T.

Activity
Cgh E 2Cg Gh 2Sg
IR Raman
--
A' 1 1 1 1 R. axa; +a ll'Y' a zz
AU 1 1 -1 -1 T.

E' 2 -1 2 -1 (Tx , Ty ) (a rex - a.y , a XY )

EU 2 -1 -2 1 (R re , R.) (are.' avz)

Activity
C. h E C. C_ e: i S: Gh S.
IR Raman
-
Ag 1 1 1 1 1 1 1 1 R. (Xxx+ay'Y' U zz
Bg 1 -1 1 -1 1 -1 1 -1 lXxx -ay1I , a xv

Eg {~
i
- i -1
-1 -i
i 1 -i
i 1 -1
-1
- !} (R x , R.) (a x .. a y.)

Au 1 1 1 1 -1 -1 -1 -1 T.
Bu 1 -1 1 -1 -1 1 -1 1

Eu {~
i -1 - i -1
- i -1 i -1
-i
i
1
1 -!} (Tx , T.)
206 Appendix 1

Activity
C5h E 2C5 2q (jh 2S: 2S:
IR Raman
--
A' 1 1 1 1 1 1 Rz axa; + a'Y'Y' a zz
A" 1 1 1 -1 -1 -1 Tz
E'I 2 2 cos 72° 2cos 144° 2 2 cos 72° 2 cos 144° (Tx , Ty)
Eil
I 2 2 cos 72° 2 cos 144° -2 -2 cos 72° -2 cos 144° (R x , R y) (a xz , ayz)

E' 2 2 cos 144° 2 cos 72° 2 2 cos 144° 2 cos 72° (aXX-ayy, a XY )
•
Eil 2 2 cos 144° 2 cos 72° -2 -2 cos 144° -2 cos 72°
•

Activity
C6h E 2C 6 2q"",C. q"",C:' (jh 2S6 2Ss S. "'" i
IR Raman
--
Ag 1 1 1 1 1 1 1 1 Rz a xx +ayy , a zz
Au 1 1 1 1 -1 -1 -1 -1 Tz
Bg 1 -1 1 -1 -1 1 -1 1
B" 1 -1 1 -1 1 -1 1 -1
Elg 2 1 -1 -2 -2 -1 1 2 Rx, Ry (tu;, a yZ

E,,, 2 1 -1 -2 2 1 -1 -2 Tx , Ty
E. u 2 -1 -1 2 2 -1 -1 2 a~-a'1l'1l' a'X1/

E." 2 -1 -1 2 -2 1 1 -2

4. The D n Groups

Activity
D. E C.(z) C.(y) C.(x)
IR Raman

A 1 1 1 1 etza: , a'1l'1l' a zz

BI 1 1 -1 -1 Tz, R z a""
B. 1 -1 1 -1 Ty, R y a xz

Bs 1 -1 -1 1 Tx • R x ayZ
Character Tables 207

Activity
Da E 2C. 3C.
IR Raman

Al 1 1 1 ax:c + (11111' a zz

A. 1 1 -1 Tz, R z

E 2 -1 0 (Tx , Ty), (R x , R y) (a~x - a yy , a OOY )

(a x.. a yz)

Activity
D. E 2C. C.(= C!) 2C; 2C;'
IR Raman

Al 1 1 1 1 1 Cixa:: +a ll1l , Clzz

A. 1 1 1 -1 -1 Tz, R.

Bl 1 -1 1 1 -1 a xx - a YII

B. 1 -1 1 -1 1 aXl/

E 2 0 -2 0 0 (Tx , TI/)' (Rx ' R II ) (a", .. a ll.)

Activity
D5 E 2C5 2q 5C.
IR Raman

Al 1 1 1 1 a",x +a llll , a ••

A. 1 1 1 -1 Tz, R z

El 2 2 cos 72° 2 cos 144° 0 (Tx , Ty), (R x , R II ) (a x.. a llz )

E. 2 2 cos 144° 2 cos 72° 0 (am - al/Y ' aXl/)

208 Appendix 1

Activity
D8 E 2Ce 2Ca C2 3C: 3C;'
IR Raman

Al 1 1 1 1 1 1 a .... + aulI ' a ••

AI 1 1 1 1 -1 -1 TI, R.

Bl 1 -1 1 -1 1 -1
BI 1 -1 1 -1 -1 1
El 2 1 -1 -2 0 0 (T"" Tu), (R." Ru) (a",., al/.)

EI 2 -1 -1 2 0 0 «(X"'' ' - (XlIV' a.",)

5. The Dnh Groups

Activity
DIA E q q Cf j 11"'11 11.,. I1v•
IR Raman

Ag 1 1 1 1 1 1 1 1 a=:,a1l'll' all

A" 1 1 1 1 -1 -1 -1 -1
B 1U 1 1 -1 -1 1 1 -1 -1 R. a.",

Blu 1 1 -1 -1 -1 -1 1 1 Ta
B lu 1 -1 1 -1 1 -1 1 -1 Rv a.,.
B 2u 1 -1 1 -1 -1 1 -1 1 Tu

Bau 1 -1 -1 1 1 -1 -1 1 R., avl

Bau 1 -1 -1 1 -1 1 1 -1 T",
Character Tables 209

Activity
D Sh E 2Cs 3C. ah 2Ss 3av
IR Raman

A'1 1 1 1 1 1 1 aa:x + ay'Y' a zz

A~' 1 1 1 -1 -1 -1
A' 1 1 -1 1 1 -1
• R.
A" 1 1 -1 -1 -1 1
• T.
E' 2 -1 0 2 -1 0 (T"" Ty) (a= - a w , a.,y)
Eil 2 -1 0 -2 1 0 (R"" R y) (ay., a",.)

Activity
D'h E 2C. C'• 2C. 2C; i 2S. ah 2a v 2ad
IR Raman

Alg 1 1 1 1 1 1 1 1 1 1 a=+ayy , a ..

AlU 1 1 1 1 1 -1 -1 -1 -1 -1
A •• 1 1 1 -1 -1 1 1 1 -1 -1 R.

A.u 1 1 1 -1 -1 -1 -1 -1 1 1 T.
Blg 1 -1 1 1 -1 1 -1 1 1 -1 aza: - a y'1l

Bl" 1 -1 1 1 -1 -1 1 -1 -1 1

B.g 1 -1 1 -1 1 1 -1 1 -1 1 a",y

B. u 1 -1 1 -1 1 -1 1 -1 1 -1
Eg 2 0 -2 0 0 2 0 -2 0 0 (R"" R y) (ay., a",.)

Eu 2 0 -2 0 0 -2 0 2 0 0 (T"" Ty )
 N
....
o

Activity
DiA E 2Ca 2q 5C. (JA 2S5 2S: 5(J~
IR Raman

A'1 1 1 1 1 1 1 1 1 a" + at/v' azz

A' 1 1 1 -1 1 1 1 -1 R.
•
E'1 2 2cos 72° 2 cos 144° 0 2 2cos 72° 2 cos 144° 0 (T." T.)
E' 2 2 cos 144° 2 cos 72° 0 2 2 cos 144° 2 cos 72° 0 (a.,. - a •• , a.,.)
•
A"
1 1 1 1 1 -1 -1 -1 -1
A" 1 1 1 -1 -1 -1 -1 1 T.
•
Eil 2 2cos 72° 2 cos 144° 0 -2 -2 cos 72° -2 cos 144° 0 (R." (a.,.. all.)
1 Rw)
Eil 2 2cos 144° 2 cos 72° 0 -2 -2 cos 144° -2 cos 72° 0
•

»
'tI
'tI
(1)
:::I
c..
x·
....
 o
:T
111
..
111
o
CD
Activity .....
D8h E 2C. 2C. CI 3C: 3C;' i 2S8 2S. (JA 3(Jd 3(J~ ~
r:1'
IR Raman iii
I/l

Au 1 1 1 1 1 1 1 1 1 1 1 1 a.,.,+all!l,a••

A zu 1 1 1 1 -1 -1 1 1 1 1 -1 -1 R.

BIg 1 -1 1 -1 1 -1 1 -1 1 -1 1 -1
Bau 1 -1 1 -1 -1 1 1 -1 1 -1 -1 1
Eu 2 1 -1 -2 0 0 2 1 -1 -2 0 0 (R~, R,,) (a,.., av.)
Eu 2 -1 -1 2 0 0 2 -1 -1 2 0 0 (au - all!l,a~)

Al,. 1 1 1 1 1 1 -1 -1 -1 -1 -1 -1
A z,. 1 1 1 1 -1 -1 -1 -1 -1 -1 1 1 T.

B l ,. 1 -1 1 -1 1 -1 -1 1 -1 1 -1 1
Bau 1 -1 1 -1 -1 1 -1 1 -1 1 1 -1

El " 2 1 -1 -2 0 0 -2 -1 1 2 0 0 (T~, TI/)

E a" 2 -1 -1 2 0 0 -2 1 1 -2 0 0

~
~
212 Appendix 1

6. Tbe D nd Groups

Activity
D'd E 2S: C'• 2C. 2ad
IR Raman

Al 1 1 1 1 1 Ci"" + Civv ' Ci..

A. 1 1 1 -1 -1 R.
BI 1 -1 1 1 -1 au -a'UlI ..

B. 1 -1 1 -1 1 T. Ci"v
E 2 0 -2 0 0 (T", T.), (R", R.) (Ci•• , Ci".)

Activity
D'd E 2C. 3C. i 2S6 3ad
IR Raman

AlU 1 1 1 1 1 1 Ci"" + Ciw ' Ci••

A•• 1 1 -1 1 1 -1 R.
Eu 2 -1 0 2 -1 0 (R", R v) (Ci",,,-Cil/V ' Cixv)'(Ci"., Civ.)

Alu 1 1 1 -1 -1 -1

A.u 1 1 -1 -1 -1 1 T.
Eu 2 -1 0 -2 1 0 (T". Tv)

Activity
D'd E 2S8 2C, 2S: C. 4C; 4ad
IR Raman

Al 1 1 1 1 1 1 1
Ci"" + Civv • Ci••
A. 1 1 1 1 1 -1 -1 R.
BI 1 -1 1 -1 1 1 -1

B. 1 -1 1 -1 1 -1 1 T.
EI 2 V2 0 -V2 -2 0 0 (T". TlI )
E. 2 0 -2 0 2 0 0 (Ci"" - Cil/v ' Ci",v)

Es 2 -V2 0 V2 -2 0 0 (R". R lI ) (Ci"•• Civ.)

 n
::T
III
.,
III

CI)
".,....
;t
0-
CD
Activity Ul

D 5d E 2C5 2q SC2 i 2S~0 2S,o Sad

IR Raman

A'g 1 1 1 1 1 1 1 1 a xx + C1. yy ' C1.zz

A 2g 1 1 1 -1 1 1 1 -1 Rz

Elg 2 2 cos 72° 2 cos 1440 0 2 2 cos 72° 2 cos 144° 0 (R x , R y ) (ayz, a zx )

E 2g 2 2 cos 1440 2 cos 72 0 0 2 2 cos 1440 2 cos 72 0 0 (a xx - a yy , a XY )

Alu 1 1 1 1 -1 -1 -1 -1

A 2u 1 1 1 -1 -1 -1 -1 1 Tz

2 2 cos 72° 2 cos 1440 0 -2 -2 cos 72 0 -2 cos 144 0 0 (Tx,Ty)

E,u

E 2u 2 2 cos 144° 2 cos 72° 0 -2 -2cos 144 0 -2 cos 72 0 0

--- ----_. . _ -

N
...w
 N
...
"'"

Activity
D. d E 2S12 2C. 2S. 2C3 2St. C. 6C; 6ad
IR Raman

Al 1 1 1 1 1 1 1 1 1 a xx + a yy ' azz
A. 1 1 1 1 1 1 1 -1 -1 Rz

Bl 1 -1 1 -1 1 -1 1 1 -1 I
B. 1 -1 1 -1 1 -1 1 -1 1 Tz

El 2 V3 1 0 -1 -V3 -2 0 0 (Tx , T y)

E. 2 1 -1 -2 -1 1 2 0 0 (a xx - a yy ' a XY )

Es 2 0 -2 0 2 0 -2 0 0

E. 2 -1 -1 2 -1 -1 2 0 0

E. 2 -V3 1 0 -1 V3 -2 0 0 (R x , R y) (ayz. a zx )

>
'0
'0
CD
:::I
C.
;C'
...
Character Tables 215

7. Tbe Sn Groups

Activity
S4 E S4 c. S:
IR Raman
---
A 1 1 1 1 Rz a xx , + a yy , azz
B 1 -1 1 -1 Tz a xx - a yy , a XY

E
{~
i
-i
-1
-1 -:} (Tz, T y )
(Rz ' R y )
(a yZ ' azz )

Activity
S6 E C. C8S i sg S6
IR Raman

Ag 1 1 1 1 1 1 Rz a zz + a yy , a zz

Eg
D
e
e*
e*
e
1
1
e
e* :*} (R z , R y )
(a zz - a yy , a ZY )'
(a yZ ' azz)
Au 1 1 1 -1 -1 -1 Tz
e e'" -1 -e
Eu
{~ e'" e -1 -e*
-e*}
-e
(Tz, Ty)

S6 = C. xi;
 N
~
Q)

i
Activity
S8 E S8 C. S"8 c. S: C." S8 7

IR Raman

A 1 1 1 1 1 1 1 1 R. (oc",,,, + OC yy , OC••)
B 1 -1 1 -1 1 -1 1 -1 T.

6 i -6* -1 -6 -i (T"" T y )
EI :*}
{~ 6* -i -6 -1 -6* i (R x , R y )

i -1 -i 1 i -1
E. - ~} (oc",,,, - OCyy , OC",y)
{! -i -1 i 1 -i -1
-6* -i 6 -1 6* i -6 }
Es (OCyz. OC,"')
{! -6 i 6* -1 6 -i -6*

6 = e''''i/8,

»
'tI
'tI
CD
::l
C.
)C'
~
Character Tables 217

8. The Cubic Groups

Activity
T E 4Ca 4q 3C2
IR Raman

A 1 1 1 1 a xx + a yy + a zz
E

F
{!
3
c
c*

0
c*
c

0
a
-1
(Tx , T y , Tz);
(a xx + a yy - 2azz ,
a xx - a yy )

(R x , R y , R z) a xy , a xz , a yz
 ~
00

Activity
T" E 4Cs 4q 3C. i 4S. 4S: 3a"
IR Raman

Ag 1 1 1 1 1 1 1 1 u"'''' + U yy + U zz

Au 1 1 1 1 -1 -1 -1 -1

e e* 1 1 e e*
Eg (u",,,, + U yy - 2uzz , u"'''' - U yy )
{: e* e 1 1 e* e :}
e e* 1 -1 -e* -e* -I}
Eu {: e* e 1 -1 e* -e -1

Fg 3 0 0 -1 3 0 0 -1 (R"" R y , R z) (u",y, u",z, uyz)

Fu 3 0 0 -1 -3 0 0 1 (T""Ty , Tz)

8 = e21ti / 3 •
>
'0
'0
CD
::l
CL
)C'
~
Character Tables 219

Activity
Tu. E 8Ca 3C! 6S, 6C1a
IR Raman

Al 1 1 1 1 1 a...+all'l/+a••

AI 1 1 1 -1 -1

E 2 -1 2 0 0 (a... + all'l/ - 2a••• a ... - a1lll)

Fl 3 0 -1 1 -1 (Rm. Ru. R.)

Fs 3 0 -1 -1 1 (T",. TII • T.) (a"",. av•• a",.)

Activity
0 E 8C. 3C. 6C4 6C';
IR Raman
---
Al 1 1 1 1 1 axx + a yy + a..
A. 1 1 1 -1 -1
(a xx + a yy - 2a...
E 2 -1 2 0 0
axx - a yy )
(Tx • T y • Tz)
FI 3 0 -1 1 -1
(R x • R y • R z)
F. 3 0 -1 -1 1 (a XY ' ayz • azx)
 N
N
o

Activity
Ok E SC. 3C. 6C4 6C~ i SS. 3ak 6S4 6aa
IR Raman

AlU 1 1 1 1 1 1 1 1 1 1 a=+allll+a••

A 2g 1 1 1 -1 -1 1 1 1 -1 -1
Eg 2 -1 2 0 0 2 -1 2 0 0 (2a= - a",,,, - a uv ' a= -- a llll )

F,g 3 0 -1 1 -1 3 0 -1 1 -I (Ra;, R v , R z )
F2g 3 0 -I -I 1 3 0 -I -I 1 (al<V, a",. , a uz )

A,u 1 1 1 1 1 -I -I -I -I -1
A 2u 1 1 1 -1 -I -I -I -I 1 1

Eu 2 -I 2 0 0 -2 1 -2 0 0 i

F,u 3 0 -I 1 -I -3 0 1 -I 1 (T"" T", Tz)

F2U 3 0 -I -1 1 -3 0 1 1 -I
»
"C
"C
CD
::I
c..

...x·
Character Tables 221

9. The C oov and D ooh Groups

Activity
Coov E ... 2q~/rp ... qZI OOl1v
IR Raman

l:+ 1 1 1 1 T. Ci... + Cin , Ci••

l:- 1 1 1 -1 R.
(T"" T,,)
II 2 2 cos!p -2 0 (Ci.,. , l4J.)
(R." R v)

LI 2 2 cos 2tp 2 0 (CL.,., - Cin , CiIW)

11' 2 2 cos 311' -2 0

 N
N
N

Activity
E ... 2C2nlrp ... qz, 00(1" i '" 2S2n lrp ••• (1/0 ooC.
D="
IR Raman

E+
q 1 1 1 1 1 1 1 1 a ... + fXw, a••
E+ 1 1 1 1 -1 -1 -1 -1 Tz
"
E-
q I 1 1 -1 1 1 1 -1 R.
E- I 1 1 -1 -1 -1 -1 1
"
IIq 2 2 cos P -2 0 2 -2 cos P -2 0 (R", R v) (a"., a v.)

II" 2 2 cos P -2 0 -2 2 cos P 2 0 (T", Tv)

LI. 2 2 cos 2p 2 0 2 2 cos 2p 2 0 (a... - a vv ' ag:v)

LI" 2 2 cos 2p 2 0 -2 -2 cos 2p -2 0

P. 2 2 cos 3p -2 0 2 -2 cos 3p -2 0

p" 2 2 cos 3p -2 0 -2 2 cos 3p 2 0

»
'0
'0
CD
:::l
c..

...x'
 Appendix 2

DESCRIPTION OF SYMBOLISM USED

IN THE INTERNATIONAL TABLES
FOR X-RAY CRYSTALLOGRAP'HY

The space group Pbca/D~Z taken from the International Tables for X-Ray
Crystallography(l) is used to describe further characteristics of the space
group (Fig. A2-1).

Pbca No. 61 m m m Orthorhombic

D2h
I5

0.-

rV(b
-0 ~0
i--
0+ 1·0 0+
c

}-b
---~----I----
,+0 0+ 1+0 ~i
0i- -0 0)- i -

.
0
I----i----I---- x(o)
-0 Ol~ <-
0+ r+G) O·

Origin al T
Number of positions, Co-ordinates of equivalent positions Conditions limiting
Wyckolf notation,
and point symmetry possible reflections

General:
8 c I x,y,z; !+x,l-y,i; x,!+y,l-z; !-x,y,t+z; hk[: No conditions
x,y,i; !-x,!+y,z; x,!-y,t+z; i+x,y,t-z. 0Ie1: k~2n
hOl: [~2n
hkO: h~2n
hOO: (h~2n)
0k0: (k~2n)
00[: (l~2n)

Special: as aboye, plus

4 b O,O,!; !.M; 0, t ,0; ! ,0,0.
} hk[: h+k,k+l, (/+h)~2n
0,0,0; !,!,O; O,U; 1.0,t.
" a

Symmetry of special projections

(001) pgm; a' ~aI2, b' ~b (IOO)pgm; b'~bI2, c'~c (010) pgm; c' ~c/2, a'-a

Fig. A2-I.
223
224 Appendix 2

The abbreviated symmetry elements are given across the top of Fig.
A2-1 at the left corner; Pbca is the Hermann-Mauguin designation, and
D~~ is the Schoenflies notation. This is followed by the space group number
(in this case No. 61 of a total of 230), followed by the "fulI" space group
symbols (these include other symmetry elements if they are present), fol-
lowed by the crystal class out of 32 (mmm) and the crystal system (out of
seven)-orthorhombic. The symbol P2 1 /b2 1 /c2 1 /a indicates the unit cell is
"primitive," that the symmetry element 21 may be associated with the crys-
tallographic axes a, b, and c respectively. The two-fold screw axes are des-
ignated as 21 and indicate that a one-half unit cell translation follows the
normal two-fold (180°) rotation. The glide planes are all perpendicular to
the respective crystallographic axes.
The top left-hand diagram symbolizes the way in which the "asymmet-
rie unit" is repeated with the unit cell (circles and plus or minus signs are
used; the plus sign indicates lying above plane of the page and the negative
sign indicates lying below the plane of the page). The upper leji-hand corner
of the rectangle is the origin, the x axis extends down the page, and the y
axis extends across the page (from left to right).
The symbols in the right-hand diagram indicate wh ich symmetry ele-
I
ments are present and their positions. The symbol represents one two-
fold screw axis perpendicular to both a-c and b-c planes located at x = 0,
z = ! and z = 0, y = !, respectively. The two-fold axis x = !, z = 0
parallel to c and perpendicular to the a-b plane is denoted by the symbol §.
The broken lines represent glide planes seen edge-on and the small circles
represent centers of symmetry.
Under the heading "conditions limiting possible reflections" the sys-
tematically absent reflections for the space group are listed.
The listing of "coordinates of equivalent positions" gives the allow-
able atom positional parameters for sites of various symmetries within the
space group.

REFERENCE

1. N. F. M. Henry and K. Lonsdale (eds.), International Tables Jor X-Ray Crystal-

lography, Vol. 1, The Kynoch Press, Birmingham, England (1965).
 Appendix 3

SITE SYMMETRIES FOR THE

230 SPACE GROUPS

The site symmetries for the 230 space groups are given. The symmetries can
be used directly for a Bravais primitive cell, and the space groups are
numbered from 1 to 230 to make for easier reference. The sequence of num-
be ring corresponds to that used in the International Tables Jor X-Ray Crystal-
lography.(1) In using these tables, it should be noted that when the site sym-
metry is C p , C pv , or C s and p = 1, 2, 3, etc., the number of sites is infinite.
Note: The site symmetry is described by several symbols. For the example

Space group 25 pmm2 C~v: 4C2v (1); 4Cs (2); CI (4)

the coefficient represents the nonequivalent sets of sites (in this case 4C2v
sites) with one equivalent site per set shown in parentheses; an infinite num-
ber of Cs sites, each having an occupation number of two equivalent atoms
and there are four such nonequivalent sets; an infinite nu mb er of Cl sites
with four equivalent sites per set. For further discussion on this subject see
Couture(3) and Irish and Brooker. (4)

Space grouplIl Site symmetries l2l

1 Pl ClI C,(l)
2 pI 0, 8Ci (l); C, (2)
3 P2 C'2 4C.(1); C, (2)
4 P2, C 22 C, (2)
5 B. or C. c'• 2C.(l); C, (2)
6 Pm Cls 2CsCl); C, (2)
7 Pb or Pe C's C, (2)
8 Bm or Cm C's Cs(l); C, (2)
9 Bb or Ce C'8 C, (2)
10 P2/m qh 8C. h(1); 4C.(2); 2C8 (2); C, (4)

225
226 Appendix 3

Appendix 3 (eontinued)

Space group(1) Site symmetries(2)

11 P2,/m qh 4Ci (2); Cs(2); C,(4)

12 B2/m Of C2/m qh 4C,h(1); 2Ci (2); 2C,(2); Cs(2); C l (4)
13 P2/b Of P2/e Cih 4Ci (2); 2C,(2); Cl (4)
14 P2 l /b Of P2 l /e qh 4Ci (2); Cl (4)
15 B2/b Of C2/e qh 4Ci (2); C,(2); C l (4)
16 P222 Dl, 8D,(l); 12C,(2); C l (4)
17 P222 l D', 4C,(2); C l (4)
18 P2 l 2l 2 Da, 2C,(2); C l (4)
19 P2 l2 l 2 l D 42 Cl (4)
20 C222 l D5, 2C,(2); C l (4)
21 C222 D6, 4D,(l); 7C,(2); C l (4)
22 F222 D7, 4D,(l); 6C,(2); Cl (4)
23 1222 D,S 4D,(1); 6C,(2); C l (4)
24 121212 1 D92 3C,(2); C l (4)
25 Pmm2 qv 4C,v(l); 4Cs(2); C l (4)
26 Pme2 l qv 2Cs(2); C l (4)
27 Pee2 qv 4C,(2); C l (4)
28 Pma2 Civ 2C,(2); Cs(2); C(4)
29 Pea2 l qv Cl (4)
30 Pne2 qv 2C,(2); C l (4)
31 Pmn2 l qv Cs(2); C l (4)
32 Pba2 qv 2C,(2); Cl (4)
33 Pna2 l qv C l (4)
34 Pnn2 ClO
2V 2C,(2); C,(4)
35 Cmm2 Cu 2C,v(1); C,(2); 2Cs(2); C l (4)
'v
36 Cme2 l Cu Cs(2); Cl (4)
'v
37 Cee2 Cl3 3C,(2); C l (4)
'v
38 Amm2 Cu 2C,v(1); 3C.(2); C l (4)
'v
39 Abm2 C15
2V 2C,(2); Cs(2); C l (4)
40 Ama2 C 12V6 C,(2); Cs(2); Cl (4)
41 Aba2 Cl7
2V C,(2); C l (4)
42 Fmm2 CIS C,v(1); C,(2); 2C.(2); C l (4)
'v
43 Fdd2 19
C'v C,(2); Cl (4)
44 Imm2 C'o 2C,v(l); 2Cs(2); Cl (4)
'v
45 Iba2 C2l
2V 2C2 (2); C l (4)
Site Symmetries for the 230 Space Groups 227

Appendix 3 (continued)

Space group(Il Site symmetries(21

461ma2 C22 C 2(2); Cs (2); C I(4)

'v
47 Pmmm D~h 8D 2h (1); 12C2v (2); 6Cs (4); C I(8)
48 Pnnn D~h 4D,(2); 2Ci (4); 6C2(4); C I (8)
49 Pccm D~h 4C2h (2); 4D 2(2); 8C,(4); Cs (4); CI (8)
50 Pban D:h 4D,(2); 2Ci (4); 6C,(4); C I(8)
51 Pmma D~h 4C'h(2); 2C'v(2); 2C2(4); 3Cs (4); CI (8)
52 Pnna Dh 2Ci (4); 2C,(4); CI(S)
53 Pmna Dh 4C'h(2); 3C,(4); Cs (4); C I(8)
54 Pcca D~h 2Ci (4); 3C2(4); C I(8)
55 Pbam D~h 4C2h (2); 2C,(4); 2Cs (4); C I (8)
56 Pccn DIO
,h 2Ci (4); 2C2(4); C I (8)
57 Pbcm D"
,h 2Ci (4); C,(4); Cs (4); C I (8)
58 Pnnm D'2
2h 4C2h (2); 2C2(4); Cs(4); C I(8)
59 Pmmn D13
2h 2C'v(2); 2Ci (4); 2Cs (4); C I (8)
60 Pbcn D14
,h 2Ci (4); C,(4); C I (8)
61 Pbca DI5
2h 2Ci (4); CI(S)
62 Pnma DI6
,h 2Ci (4); Cs (4); C I (8)
63 Cmcm D17
2h 2C'h(2); C'v(2); C i (4); C,(4); 2Cs (4); CI(8)
64 Cmca DIS
2h 2C 2h (2); C i (4); 2C 2(4); Cs (4); C i (8)
65 Cmmm DI9
2h 4D'h(l); 2C2h (2); 6C2v (2); C2(4); 4Cs (4); CI (8)
66 Cccm D20
2h 2D 2(2); 4C'h(2); 5C2(4); Cs (4); C,(8)
67 Cmma D21 2D,(2); 4C'h(2); C 2v (2); 5C2(4); 2Cs (4); C I(8)
'h
68 Ccca D 22
2h 2D 2(2); 2Ci (4); 4C2(4); CI(S)
69 Fmmm D'3
2h 2D'h(1); 3C2h (2); D,(2); 3C2V (2); 3C2(4); 3C8 (4); CI(S)
70 Fddd D2.
2ft 2D 2(2); 2Ci (4); 3C2(4); C I (8)
71 Immm D25
2ft 4D 2ft (l); 6C2V (2); C i (4); 3Cs (4); C,(8)
72 Ibam D'·
,ft 2D 2(2); 2C2h (2); C i (4); 4C2(4); Cs (4); C,(8)
73 Ibca D27
2ft 2Ci (4); 3C2(4); C I (8)
741mma D's
,ft 4C2h (2); C 2v (2); 2C2(4); 2Cs(4); C I(8)
75 P4 Cl 2C.(1); C 2(2); C I (4)
•
76 P41 C2
• C I (4)
77 P4 2 q 3C2(2); C I (4)
78 P4 3
•
C' C I (4)
79 14
•
C5 C.(l); C 2(2); CI (4)
80 141
•
C· C,(2); C I (4)
228 Appendix 3

Appendix 3 (continued)

Space groupCl) Site symmetries (2 )

SI P4 SI
• 4S.(1); 3C2(2); C 1 (4)
S2 14 S2
• 4S.(1); 2C2(2); C 1 (4)
S3 P4/m Ch 4C. h (l); 2C 2h (2); 2C.(2); C 2(4); 2Cs(4); CI(S)
S4 P4 2/m C:h 4C2h (2); 2S.(2); 3C2(4); Cs(4); C 1 (S)
S5 P4/n C:h 2S.(2); C.(2); 2Ci (4); C 2(4); C 1 (S)
S6 P4 2/n C:h 2S 4(2); 2Ci (4); 2C2(4); C 1 (S)
87 14/m qh 2C4h (1); C 2h (2); S.(2); C 4(2); C i (4); C 2(4); Cs(4); C 1 (S)
SS 141 /a C:h 2S.(2); 2Ci (4); C 2(4); C 1 (S)
DI
S9 P422
•
D2
4D.(1); 2D 2(2); 2C.(2); 7C2(4); CI(S)
90 P42 12
• 2D 2(2); C 4(2); 3C2(4); CI(S)
Da
91 P4 122
• 3C2(4); CI(S)
92 P4 12 1 2 D' C 2(4); C 1 (S)
•
D5
93 P4 222
• 6D 2(2); 9C2(4); C1 (S)
94 P4 221 2
•
D6 2D 2(2); 4C2(4); CI(S)
95 P4 3 22
•
D'
D8
3C2(4); C 1 (S)
96 P4 3 2 12 4 C 2(4); C 1 (S)
97 1422 D9 2D 4(1); 2D 2(2); C.(2); 5C2(4); C 1 (S)
•
D IO
9S 141 22
• 2D 2(2); 4C2(4); C1 (S)
99 P4mm CL 2C4v (l); C 2v (2); 3Cs(4); C 1 (S)
100 P4bm C:v C.(2); C 2v (2); Cs(4); C1 (S)
101 P4 2cm C:v 2C2V (2); C 2(4); Cs(4); CI(S)
102 P4 2nm C:v C 2v (2); C 2(4); Cs(4); C 1 (S)
103 P4cc C!v 2C.(2); C 2(4); C 1 (S)
104 P4nc C:v C.(2); C 2(4); C 1 (S)
105 P4 2mc C1v 3C2V (2); 2Cs(4); C 1 (S)
106 P4 2bc C:v 2C2(4); CI(S)
10714mm C:v C. v(1); C 2v (2); 2Cs(4); C 1 (S)
lOS 14cm CIO
.v C.(2); C 2v (2); C.(4); C1 (S)
109141md Cu
.V C 2v (2); Cs( 4); Cl (S)
110 14 1 cd Cl2
.v C 2(4); C1 (S)
111 P42m D~d 4D 2d (1); 2D 2(2); 2C2v (2); 5C 2(4); Cs(4); C 1 (S)
112 P42c D: d 4D 2(2); 2S.(2); 7C2(4); C1 (S)
113 P42,m D~d 2S.(2); C 2v (2); C 2 (4); Cs(4); C 1 (S)
114 P42 1 c D~d 2S.(2); 2C 2(4); C 1 (S)
115 P4m2 D~d 4D 2d (I); 3C2V (2); 2C2(4); 2Cs(4); C 1 (S)
Site Symmetries for the 230 Space Groups 229

Appendix 3 (continued)

Space group(1) Site symmetries(')

116 P4c2 D:d 2D.(2); 2S.(2); 5C,(4); Cl(S)

117 P4b2 D~ä 2S.(2); 2D.(2); 4C,(4); Cl(S)
l1S P4n2 D~ä 2S.(2); 2D.(2); 4C,(4); Cl(S)
11914m2 D:ä 4D'd(1); 2C'v(2); 2C,(4); C.(4); Cl(S)
120 14c2 Dl O D.(2); 2S.(2); D,(2); 4C,(4); C, (8)
'ä
121 142m DU,ä 2D. ä(1); D,(2); S.(2); C'v(2); 3C.(4); C.(4); Cl(S)
122142d l2
D 'd 2S.(2); 2C,(4); Cl(S)
123 P4/mmm Dh 4D.,,(1); 2D.,,(2); 2C4V (2); 7C'v(4); 5C.(S); C, (16)
124 P4/mcc Dh D.(2); C.,,(2); D.(2); C.,,(2); C,,,(4); D,(4); 2C.(4);
4C,(S); C.(S); C, (16)
125 P4/nbm Dh 2D.(2); 2D. ä(2); 2C,,,(4); C.(4); C. v(4); 4C.(S);
C.(S); C, (16)
126 P4/nnc Dh 2D.(2); D.(4); S.(4); C,(4); Ct (8); 4C.(S); Cl(S)
127 P4/mbm Dh 2C,,,(2); 2D,,,(2); C,(4); 3C'v(4); 3C.(S); C, (16)
12S P4/mnc D:" 2C,,,(2); C. h(4); D.(4); C.(4); 2C,(S); C.(S); C, (16)
129 P4/nmm Dh 2D. a(2); C. v(2); 2C,,,(4); C. v(4); 2C.(S); 2C.(S);
Cl (16)
130 P4/ncc D!" D,(4); S,(4); C,(4); Ct(S); 2C,(S); Cl (16)
131 P4,/mmc Dh 4D.,,(2); 2D,a(2); 7C'v(4); C,(S); 3C.(S); C, (16)
132 P42/mcm Dl.10O D. h(2); D. a(2); D'h(2); D 2d (2); D.(4); C2h(4);
4C2V (4); 3C,(S); 2C.(S); C, (16)
133 P4./nbc DU
." 3D.(4); S,(4); Ct(S); 5C,(S); C, (16)
134 P4,/nnm
."
D" 2D. d(2); 2D.(4); 2C. h(4); C 2v (4); 5C.(S); C.(S); C, (16)
135 P4./mbc
."
Dl 3 C.,,(4); S,(4); C.,,(4); D,(4); 3C.(S); C.(S); C, (16)
136 P4./mnm
."
Dl' 2D,,,(2); C.,,(4); S,(4); 3C'v(4); C.(S); 2C.(8); C, (16)
137 P4./nmc
."
D l5 2D. a(2); 2C2V (4); C;(S); C.(8); C.(S); C, (16)
13S P4./ncm
13914/mmm
Dl
."
Dl7
ß
D.(4); S.(4); 2C2h (4); C'v(4); 3C,(8); C.(S); C, (16)
2D.,,(I); D.,,(2); D'd(2); C'v(2); C,,,(4); 4C.v(4);
,10
C,(S); 3C.(S); C, (16)
140 14/mcm
."
Dl S D,(2); D 2d (2); C,,,(2); D'h(2); C,,,(4); C.(4);
2C. v(4); 2C.(S); 2C.(8); C, (16)
Dl9
141 14,/amd
."
D20
2D. d(2); 2C,,,(4); C'v(4); 2C.(S); C.(S); C, (16)
142 14,/acd ,10 S,(4); D.(4); C;(8); 3C.(S); C, (16)
143 P3 Cl3 3C.(1); C, (3)
144 P3, C'
• C, (3)
145 P3. C·3 C, (3)
230 Appendix 3

Appendix 3 (continued)

Space group(1) Site symmetries(')

146 R3 C'3 C3 (1); C,(3)

147 P3 qi 2Cgi (1); 2Cg(2); 2Ci (3); C,(6)
148 R3 Ci, 2C3i (1); Cs (2); 2Ci (3); C,(6)
149 P312 D'3 6D g (1); 3Cg(2); 2C.(3); C,(6)
150 P321 D23 2D g (1); 2C3 (2); 2C.(3); C,(6)
151 P3,12 D33 2C.(3); C,(6)
152 P3,21 D'3 2C.(3); C,(6)
153 P3.12 D5S 2C.(3); C,(6)
154 P3.21 D·3 2C.(3); C,(6)
155 R32 D 73 2D.(1); C.(2); 2C.(3); C,(6)
156 P3m1 qv 3Csv (1); C.(3); C,(6)
157 P31m Civ C3V (1); Cs (2); C.(3); C,(6)
158 P3c1 Civ 3C3 (2); C,(6)
159 P31c C:v 2C3 (2); C,(6)
160 R3m qv C3v (1); C.(3); C,(6)
161 R3c qv C3 (2); C,(6)
162 P31m D~rL 2D srL (1); 2D.(2); C. v(2); 2C. h(3); C3 (4); 2C2(6);
C.(6); C,(12)
163 P31c D~rL D s(2); Csi (2); 2D3 (2); 2Cs (4); Ci (6); C.(6); C,(12)
164 P3m1 D:rL 2D srL (1); 2C. v(2); 2C2,,(3); 2C.(6); C.(6); C,(12)
165 P3c1 D~rL D s(2); C. i (2); 2Cs (4); Ci (6); C,(6); C.(12)
166 R3m D:rL 2D srL (1); Csv (2); 2C. h(3); 2C.(6); C.(6); C,(12)
167 R3c D:rL D 3 (2); Csi (2); Cs (4); C,(6); C.(6); C,(12)
168 P6
•
C' C.(l); C s(2); C2(3); C,(6)
169 P6, C'6 C,(6)
CS
170 P6.
• C,(6)
171 P6. q 2C2(3); C,(6)
C·
172 P6.
• 2C.(3); C,(6)
173 P6. q 2C3 (2); C,(6)
174 P6 q" 6C3 ,,(1); 3C3 (2); 2C.(3); C,(6)
175 P6/m Ch 2C. h(1); 2C3 ,,(2); C.(2); 2C2,,(3); Cg(4); C.(6);
2C.(6);" C,(12)
176 P6 3 /m C:h Csh (2); C3 ,(2); 2C3 ,,(2); 2Cg(4); Ci (6); C.(6); C,(12)
173 P622 D'
D2
• 2D.(1); 2D 3 (2); C.(2); 2D.(3); C.(4); 5C2(6); C,(12)
178 P6,22
• 2C.(6); C,(12) "
Site Symmetries for the 230 Space Groups 231

Appendix 3 (continued)

Space group(') Site symmetries(')

D3
179 P6522
• 2C.(6); C,(12)
D4
180 P6.22
• 4D.(3); 6C.(6); C,(l2)
181 P6 422 D56 4D 2 (3); 6C 2 (6); C,(12)
182 P6 322 D·6 4D 3(2); 2C3(4); 2C.(6); C,(12)
183 P6mm qv C. v(l); C 3v (2); C. v(3); C. v(3); 2Cs(6); C,(l2)
184 P6cc qv C.(2); C3(4); C 2(6); C, (l2)
185 P6 3cm C:v C 3v (2); C 3(4); Cs(6); C,(12)
186 P6 3mc C:v 2C3V (2); Cs(6); C,(12)
187 P6m2 D~h 6D 3h (l); 3C3V (2); 2C,v(3); 3C.(6); C, (12)
188 P6c2 D~h D 3(2); C 3h (2); D 3(2); C 3h (2); D 3(2); C 3h (2); 3C3(4);
C 2(6); C.(6); C,(12)
189 P62m D:h 2D ah (1); 2C3h (2); C 3v (2); 2C. v(3); C 3(4); 3C.(6);
C,(12)
190 P62c D!h D 3(2); 3C3h (2); 2C3(4); C.(6); C s(6); C,(l2)
191 P6/mmm Dh 2D. h(1); 2D 3h (2); C. v(2); 2D'h(3); C 3v (4); 5C'v(6);
4C.(12); C,(l2)
192 P6/mcc D: h D.(2); C. h(2); D 3(4); C ah (4); C 6 (4); D.(6); C 2h (6);
C 3(8); 3C,(l2); C.(l2); C,(24)
193 P63/mcm D:h D ah (2); D 3d (2); C ah (4); D 3(4); C.(4); C 2h (6); C. v(6);
C 3(8); C.(12); 2C2 (l2); C,(24)
194 P6 3/mmc Dih D ad (2); 3D 3h (2); 2C3V (4); C 2h (6); C. v(6); C 2 (l2);
2C8 (12); C,(24)
195 P23 T' 2T(1); 2D 2(3); C 3(4); 4C.(6); C,(12)
196 F23 T' 4T(1); C3(4); 2C.(6); C,(12)
197 123 T3 T(l); D,(2); C 3(4); 2C.(6); C,(12)
198 P2,3 T4 C 3(4); C,(12)
199 12,3 T6 C 3(4); C.(6); C, (12)
200 Pm3 Tl 2Th(1); 2D. h(3); 4C2V (6); C 3(8); 2C.(12); C,(24)
201 Pn3 T'h T(2); 2C3i (4); D,(6); C 3(8); 2C 2 (12); C,(24)
202 Fm3 T~ 2Th(l); T(2); C. h(6); C. v(6); C 3(8); C.(12); C.(12);
C,(24)
203 Fd3 Tfi 2T(2); 2C3i (4); C 3(8);C.(12); C,(24)
204 1m3 Tt Th(1); D'h(3); C3i (4); 2C'v(6); C3(8); C8 (12); C,(24)
205 Pa3 T~ 2C3i (4); C 3(8); C, (24)
206Ia3 TX 2C3i (4); C 3(8); C 2(12); C,(24)
207 P432 0' 20(1); 2D 4(3); 2C.(6); C 3(8); 3C,(12); C,(24)
232 Appendix 3

Appendix 3 (continued)

Space group(l) Site symmetries(2)

208 P4.32 02 T(2); 2D 3 (4); 3D.(6); Ca (8); 5C.(12); C1 (24)

209 F432 03 20(1); T(2); D 2 (6); C.(6); C3 (8); 3C2 (12); C1 (24)
210 F4 1 32 O' 2T(2); 2D a (4); C3 (8); 2C2 (12); C1 (24)
211 1432 0 5 0(1); D.(3); D a(4); D 2 (6); C.(6); Ca(8); 3C2 (12);
CI (24)
212 P4 3 32 0 6 2D 3 (4); C3 (8); C 2 (12); C1 (24)
213 P4 132 O' 2D.(4); C3 (8); C.(12); C1 (24)
214 14132 08 2D 3 (4); 2D.(6); C3 (8); 3C2 (12); C1 (24)
215 P43m Ta 2Ta(1); 2D 2d (3); Ca.(4); 2C2.(6); C.(12); C.(12);
C1 (24)
216 F43m TJ 4Ta(1); C3 .(4); 2C2.(6); C.(12); C1 (24)
217 143m Tl T a(1); D. a(3); C3 .(4); 8.(6); C •• (6); C.(12); C.(12);
C1 (24)
218 P43n n T(2); D 2 (6); 28.(6); C3 (8); 3C.(12); C1 (24)
219 F43c Tj 2T(2); 28.(6); C3 (8); 2C2 (12); C1 (24)
220 143d T3 2S.(6); C3 (8); C.(12); C1 (24)
221 Pm3m 01 20 h (1); 2D4h (3); 2C. v (6); Cav (8); 3C2v (12); 3C.(24);
C1 (48)
222 Pn3n O~ 0(2); D.(6); C31 (8); S.(12); C.(12); Ca (16); 2C2 (24);
C1 (48)
223 Pm3n O~ T h (2); D 2h (6); 2D. a(6); D.(8); 3C. v (12); C.(16);
C 2 (24); C.(24); C1 (48)
224 Pn3m ot T a(2); 2D. a(4); D 2d (6); C•• (8); D 2 (12); C ••(12);
3C2 (24); C1 (48)
225 Fm3m O~ 20 h (1); T a(2); D. h (6); C. v (6); C av (8); 3C. v (12);
2Cs (24); C1 (48)
226 Fd3c O~ 0(2);. T h (2); D. a(6); C. h (6); C. v (12); C.(12); C.(16);
C.(24); C.(24); C1 (48)
227 Fd3m 01. 2Td (2); 2Dad (4); C av (8); C •• (12); C.(24); C.(24);
C1 (48)
228 Fd3c O~ T(4); D a(8); Cal (8); S.(12); C.(16); 2C.(24); C1(48)
2291m3m O~ Oh(l); D. h (3); D. d (4); D. d (6); C•• (6); Cav (8);
2C2.(12); C.(24); 2Cs (24); C, (48)
230 la3d 01° C.1(8); D.(8); D.(12); S.(12); Ca(16); 2C.(24);
C1 (48)

Note the following equivalent nomenclatures: Ci == S•• C. == C1h • D2 == V. D 2h ~ V h •

D 2a == Vd • and C.! == S6.
Site Symmetries for the 230 Space Groups 233

REFERENCES

1. N. F. M. Henry and K. Lonsdale (eds.), International Tables/or X-Ray Crystallography,

Vol. 1, Kynoch Press, Birmingham, England (1965).
2. R. S. Halford, J. Chern. Phys., 14:8 (1946).
3. L. Couture, J. Chern. Phys., 15:153 (1947).
4. D. E. Irish and M. H. Brooker, Appl. Spec., 27:395 (1973),
 Appendix 4

CORRELATION TABLES

The correlation tables which follow are heipful in determining the site group
reiating to the moIecuIar point group. The tables give the correiations be-
tween species of a group and a subgroup. We wish to express our gratitude
to St. Martin's Press forpermission to reproduce these tables from the book
by D. M. Adams,(!) and to W. G. Fateley et al. for the use of their compre-
hensive tables.(2)

C. C. C. Ca C_ Cl D. CZ CY C'"• Da Ca C.
• •
-- -- --
A A A A A A A A A A Al A A
B A B A B A Bl A B B A. A B
E 2B El E 2B 2A B. B A B E E A+B
E. E 2A 2A Ba B B A

C" C"2
D.
C~
D.
•
D. C. C.
C~
C. C. D5 C5 C.

Al A A A A A A Al A A
A. Bl Bl A A B B A. A B
Bl A Bl B A A B El El A+B
B. Bl A B A B A E. E_ A+B
E B. + Ba B. + Ba E 2B A+B A+B

_
C' C" C' C"
D. C.
• •
Da Da D_ Ca C_ C_
•
C_

Al A Al Al A A A A A
A. A A_ A_ Bl A A B B
Bl B Al A_ B_ A B A B
B. B A_ Al Ba A B B A
El El E E B_ + Ba E 2B A+B A+B
E_ E_ E E A + Bl E 2A A+B A+B

235
236 Appendix 4

G(zx) G(Yz)
C. v C. C. C. C 3v C3 C.

Al A A' A' Al A A'

A. A A" ftt" A. A A"
Bl B A' A" E E A' +A"
B. B A" A'

Gv Gd, Gv Gd,
C. v C. C. v C. v C. C. C.

Al A Al Al A A' A'
A. A A. A. A A" A"
Bl B Al A. A A' A"
B. B A. Al A A" A'
E E Bl + B. Bl + B. 2B" A' +A" A'+A"

C sv Cs C.

Al A A'
A. A A"
El El A'+A"
E. E. A'+A"

Gv Gd, G v ->- G(ZX) Gv Gd,

Cs• Cs C 3v C 3v C. v C3 C. C. C.

Al A Al Al Al A A A' A'
A. A A. A. A. A A A" A"
Bl B Al A. Bl A B tA' A"
B. B A. Al B. A B A" A'
El El E E Bl + B. E 2B A'+A" A'+A"
E. E. E E Al + A. E 2A A'+A" A'+A"

C. h C. C. Ci C3h C3 C. Cl

Ag A A' Ag A' A A' A

Bg B A" Ag E' E 2A' 2A
Au A A" Au A" A A" A
Bu B A' Au E" E 2A" 2A
Correlation Tables 237

C. h C. S. C. h C. C. Ci Cl C. h C. C. Cl

Ag A A Ag A A' Ag A A' A A' A

Bg B B Ag A A' Ag A Et' EI 2A' 2A
Eg E E 2Bg 2B 2A u 2Ag 2A E.' E. 2A' 2A
Au A B Au A AU Au A AU A AU A
Bu B A Au A AU Au A E{' EI 2A u 2A
E E 2Bu 2B 2A' 2A u 2A EU 2A u 2A
Eu • E.

C 6h C. C3h S. C. h C3 C. Cs Ci Cl

Ag A A' Ag Ag A A A' Ag A
Bg B AU Ag Bg A B AU Ag A
Elg EI EU Eg 2Bg E 2B 2A u 2Ag 2A
E.g E. E' Eg 2Ag E 2A 2A' 2Ag 2A
Au A AU Au Au A A AU Au A
Bu B A' Au Bu A B A' Au A
EIU EI E' Eu 2Bu E 2B 2A' 2A u 2A
E.u E. EU Eu 2A u E 2A 2A u 2A u 2A

C.(z) C.(y) C.(x) C.(z) C.(y) C.(x)

D' h D. C." C." C." C. h C. h C. h

Ag A Al Al Al Ag Ag Ag
Blg BI A. B. BI Ag Bg Bg
B.g B. BI A. B. Bg Ag Bg
B3g B3 B. BI A. Bg Bg Ag
Au A A. A. A. Au Au Au
Bw BI Al BI B. Au Bu Bu
B.u B. B. Al BI Bu Au Bu
B3U B3 BI B. Al Bu Bu Au

D' h C.(z) C.(y) C.(x) a(xy) a(zx) a(yz)

(cont.) C. C. C. Cs Cs Cs Ci

Ag A A A A' A' A' Ag

Blg A B B A' AU AU Ag
B.g B A B AU A' AU Ag
B3g B B A AU AU A' Ag
Au A A A AU AU AU Au
Bw A B B AU A' A' Au
B2U B A B A' AU A' Au
B3U B B A A' A' AU Au
238 Appendix 4

ah --+ av(zy) ah av
D3h Cah D3 C3V C2v C3 C2 Cs Cs

A,' A' A, A, A, A A A' A'

A2' A' A2 A2 B2 A B A' A"
E' E' E E A, + B2 E A+B 2A' A' + A"
A" A" A, A2 A2 A A A" A'{l
1
A" A" A2 A, B, A B A" A'
• + A"
E" E" E E A. + B, E A+B 2A" A'

C'2 C"
D4h D4 D2d
C~ --+ C~ C~' -+ C~
D2d C 4n C 4h D2h
•
D2h C4 S4

Alg Al A, Al Al Ag Ag Ag A A
A2g A2 A2 A2 A2 Ag B,g Blg A A
Blg BI BI B2 B, Bg Ag B,g B B
B2g B2 B2 B, B2 Bg Blg Ag B B
Eg E E E E Eg B2g + B3g B2g + Bag E E
AlU A, BI BI A2 Au Au Au A B
A2u A2 B2 B. A, Au Blu B1u, A B
BlU B, Al A2 B. Bu Au BlU B A
B2u B2 A2 A, B, Bu B,u Au B A
Eu E E E E Eu Bou + B3u B2u + B3u E E

D4h C'2 C"2 C 2 , crv C2 , erd C'2 C"2

(cant.) D2 D. C2v C2V C2V C2v

Arg A A Al Al Al A,
A2g BI 81 A2 A2 BI BI
B,g A B, A, A. Al 8,
B2g B, A A2 Al B, A,
Eg B2 + B3 B2 + B, B, + B2 BI + B2 A2 + B2 A. + B2
AlU A A A2 A2 A. A2
Aou BI BI A, A, B2 B2
B,u A B, A2 A, A2 B2
B2u B, A Al A2 B2 A2
Eu B2 + B3 B2 + B, BI + B 2 B, + B2 Al + BI Al + BI
Correlation Tables 239

C. Cu C' C"
D 4h
(cont.) C. h
C~
C. h
•
C. h
C.
C.
•
C.
•
C,
Gh

C.
Gv

C.
Gd

C. Ci

Alg Ag Ag Ag A A A A' A' A' Ag

A.g Ag Bg Bg A B B A' A" A" Ag
Blg Ag Ag Bg A A B A' A' A" Ag
B.g Ag Bg Ag A B A A' A" A' Ag
Eg 2Bg Ag + Bg Ag + Bg 2B A+B A+B 2A" A'+A" A'+A" 2Ag
AlU Au Au Au A A A A" A" A" Au
A.u Au Bu Bu A B B A" A' A' Au
BlU Au Au Bu A A B A" A" A' Au
B,u Au Bu Au A B A A" A' A" Au
Eu 2Bu Au + Bu Au + Bu 2B A+B A+B 2A' A'+A" A'+A" 2A u

Gh -+ G(zx) Gh Gv

D' h D. C.. C. h C. C,v C. C. C.

A'1 Al Al A' A Al A A' A'

A' A. A. A' A B, B A' A"
•
E{ E, E, E'1 E, Al + B, A+B 2A' A'+A"
E'• E. E, E'
• E. Al + B, A+B 2A' A'+A"
A"1 Al A. A" A A. A A" A"
A"• A. Al A" A B. B A" A'
E{' E, El E"1 E, A. + B. A+B 2A" A'+A"
E"
• E. E. E"
• E. A. + B. A+B 2A" A' +A"

G h -+ a(xy)
C' c" C" C' G v -+ G(YZ)
D6h D.
• • • •
D3h D3h C. v C 6h D3d Dad D' h

A,g Al A'1 A~ Al Ag A,g Alg Ag

A.g A. A' A' A. Ag A.g A.g B,g
B,g B, A"
• •
A" B. Bg A.g A,g B.g
B. A"
1
• B, Bg A,g A.g Bag
B'g • A{'
E,g E, E" E" E, E,g Eg Eg B.g + Bag
E.g E. E' E' E. E2g Eg Eg Ag + B,g
AlU Al A{' AU1 A. Au Alu AlU Au
A2 AU A" Al Au A,u A.u B,u
A 2U
BlU B,
• A'
• B, Bu
A~
• A.u AlU B.u
B.u B. A' A'1 B. Bu AlU A.u Bau
E,u E,
•
E' E' E, E,u Eu Eu B2a + Bau
E.u E. E" E" E2 E.u Eu Eu Au + BlU
240 Appendix 4

D6h C'2 C"2 (Jv (Jd

(cant.) C6 C 3h D3 D3 C 3V C 3V S6 D2

Aig A A' Al Al Al Al Ag A
A2g A A' A2 A2 A 2 A2 Ag BI
Big B A" Al A2 A 2 Al Ag B2
B2g B A" A2 Al Al A2 Ag B3
Eig EI E" E E E E Eg B2 -+- B3
E2g E2 E' E E E E Eg A -+-BI
AlU A A" Al Al A, A2 All A
A 2u A A" A2 A2 Al Al Au BI
BlU B A' Al A 2 Al A2 Au B2
B2U B A' A2 Al A 2 Al Au Bs
Elu EI E' E E E E Eu B 2 -+- B3
E2u E2 E" E E E E Eu A -+- BI

D6h C2 C'2 C"2 C2 C'2 C"2 C2

(cant.) C 2V C 2V C 2V C 2h C 2h C 2h C3 C2

Alg Al Al Al Ag Ag Ag A A
A2g A2 BI BI Ag Bg Bg A A
Big BI A2 B2 Bg Ag . Bg A B
B2g B2 B2 A2 Bg Bg Ag A B
Eig BI -+- B2 A2 -+- B2 A2 -+-B 2 2Bg Ag -+- Bg Ag -+- Bg E 2B
E2g Al -+- A2 Al -+- BI Al -+-BI 2A g Ag -+- Bg Ag -+- Bg E 2A
AlU A2 A2 A2 Au Au Au A A
A2u Al BI B2 Au Bu Bu A A
Bw B2 Al BI Bu Au Bu A B
B2u BI B2 Al Bu Bu Au A B
Elu B2 + BI Al + B2 Al -+- BI 2Bu Au + Bu Au -+- Bu E 2B
E2U A2 -+- Al A2 +BI A2 + B2 2A u Au + Bu Au + Bu E 2A
Correlation Tables 241

C' C"
D'h
(cant.)
• • (Jh

Cs
(Ja

Cs
(Jv

Cs
C. C. Ci

A,g A A A' A' A' Ag

A2g B B A' A" A" Ag
Btg A B A" A' A" Ag
B2g B A A" A" A' Ag
E,g A+B A+B 2A" A' +A" A' +A" 2A g
E2g A+B A+B 2A' A' + A" A' + A" 2A g
AlU A A A" A" A" Au
A 2U B B A" A' A' Au
BlU A B A' A" A' Au
B2U B A A' A' A" Au
ElU A+B A+B 2A' A' +A" A' +A" 2A u
E.u A+B A+B 2A" A' + A" A' +A" 2A u

A' E'I E'a E"a

• E'2 A~f A~' E~f E~'

C2 -+ C2(z) C2 C'2
D2d S. D2 C2V C2 C2 Cs

A, A A A, A A A'
A2 A BI A2 A B A"
BI B A A2 A A A"
B2 B BI Al A B A'
E E B2 + Ba B, + B2 2B A+B A' +A"

Dad Da C 3V S, Ca C 2h C2 Cs Ci

A,g Al Al Ag A Ag A A' Ag
A2g A2 A2 Ag A Bg B A" Ag
Eg E E Eg E Ag + Bg A+B A' +A" 2A g
AlU A, A2 Au A Au A A" Au
A 2U A2 Al Au A Bu B A' Au
Eu E E Eu E Au + Bu A+B A' +A" 2A u
242 Appendix 4

C. C'2
D' d D. C.V SB C. C2V C2 C2 Cs

Al Al Al A A Al A A A'
A2 A2 A_ A A A2 A B A"
BI Al A2 B A A2 A A A"
B2 A2 Al B A Al A B A'
EI E E EI E BI + B2 2B A+B A' +A"
E2 BI + B2 BI + B2 E2 2B Al + A2 2A A+B A' +A"
Ea E E Ea E BI + B2 2B A+B A' + A"

D5d D5 C5V C5 C2 Cs Ci

Alg Al Al A A A' Ag
A2g A 2 A2 A B A" Ag
Elg EI EI EI A+B A' +A" 2Ag
E2g E2 E2 E2 A+B A' +A" 2Ag
AlU Al A 2 A A A" Au
A2u A 2 Al A B A' Au
EIU EI EI EI A+B A' +A" 2A u
E2U E2 E2 E2 A+B A' +A" 2A u

D. d D. C. v C. D 2d Da C av

Al Al Al A Al Al Al
A2 A2 A2 A A2 A2 A2
BI Al A2 A BI Al A2
B2 A2 Al A B2 A_ Al
EI EI EI EI E E E
E2 E2 E2 E2 B, + B2 E E
Ea B, + B2 B, + B2 2B E A, + A2 Al + A2
E. E2 E2 E2 Al + A2 E E
E5 E, E, E, E E E
Correlation Tables 243

D6d C. C'
•
(cant.) D. C. v S. C3 C. C. Cs

Al A Al A A A A A'
A. Bl A. A A B A"
Bl A A. B A A A A"
B. BI Al B A A B A'
EI B. + B3 BI + B. E E 2B A+B A' +A"
E. A +BI Al + A. 2B E 2A A+B A' +A"
E3 B. + B3 BI + B. E 2A 2B A+B A' +A"
E. A + BI Al + A. 2A E 2A A+B A' +A"
E5 B. + BI BI + B. E E 2B A+B A' +A"

S. C. Cl S. C3 Ci Cl SB C. C. Cl

A A A Ag A Ag A A A A A
B A A Eg E 2A g 2A B A A A
E 2B 2A Au A Au A EI E 2B 2A
Eu E 2A u 2A E. 2B 2A 2A
E3 E 2B 2A

T D. C3 C.

A A A A A
E 2A E 2A 2A
F BI + B. + B3 A +E A + 2B 3A

Th T D' h S. D.

Ag A Ag Ag A
Eg E 2A g Eg 2A
Fg F B lg + B.g + B3g Ag + Eg BI + B. + B3
Au A Au Au A
Eu E 2A u Eu 2A
Fu F Blu + B.u + B 3u Au + Eu BI + B. + Ba
244 Appendix 4

Th
(cont.) C.v C. h Ca C. Cs Ci Cl

Ag Al Ag A A A' Ag A
Eg 2A l 2A. E 2A 2A' 2Ag 2A
Fg A. + Bl + B. Ag + 2Bg A+E A +2B A' + 2A" 3Ag 3A
Au A. Au A A A" Au A
Eu 2A. 2A u E 2A 2A" 2A u 2A
Fu Al + Bl + B. Au +2Bu A+E A + 2B 2A' +A" 3A u 3A

Ta T D.a C av S. D. C.v

Al A Al Al A A Al
As A Bl A. B A A.
E E Al + Bl E A+B 2A Al + A.
Fl F A. + E A. +E A+E Bl + B. + Ba A. + Bl + B.
F. F B. +E Al + E B+E Bl + B. + Ba Bl + B. + Ba

Ta
(cont.) Ca C. Cs

Al A A A'
A. A A A"
E E 2A A'+A"
Fl A+E A +2B A' +2A"
F. A+E A +2B 2A' +A"

3C. C., 2C~

0 T D. Da C. D. D.

Al A Al Al A A A
A. A Bl A. B A Bl
E E Al + Bl E A+B 2A A +Bl
Fl F A. +E A. + E A+E Bl + B. + Ba Bl + B. + Ba
F. F B.+E Al + E B+E Bl + B. + Ba A + B. + Ba
Correlation Tables 245

0
(cont.) C3 C2 C2

Al A A A
A2 A A B
E E 2A A+B
Fl A+E A + 2B A + 2B
F2 A+E A +2B 2A +B

Oh* 0 Td Th T D 4h D 3d D 4d C 3V D3 D 3i == S6

A lg Al Al Ag A A lg A lg Al. Al Al Ag
A 2g A2 A2 Ag A Blg A 2g B lg A2 A2 Ag
Eg E E Eg E A lg + Blg Eg A lg + B lg E E Eg
Flg Fl Fl Fg F A 2g + Eg A 2g + Eg A 2g + Eg A 2 +E A 2 +E Ag+Eg
F2g F2 F, Fg F B2g +Eg A lg + Eg B'g + Eg Al +E Al+E Ag+Eg
AlU Al A2 Au A AlU AlU AlU A2 Al Au
A,u A, Al Au A B lU A 2u B lu Al A2 Au
Eu E E Eu E Alu +Blu Eu AlU +BlU E E Eu
F lu Fl F2 Fu F A 2u +Eu A'u+Eu A'u+Eu Al +E A,+E Au+Eu
F2U F2 Fl Fu F B 2u + Eu Alu + Eu B,u + Eu A 2 +E Al +E Au+Eu

°h C" Gd C;, Gh
(cont.) C3 D 2d D'd C 4V D4 C4h S4 C4

A lg A Al Al Al Al Ag A A
A'g A Bl B, Bl Bl Bg B B
Eg E Al + B l Al + B, Al + B l Al + B l Ag + Bg A+B A+B
Flg A+E A2 + E A, + E A2 + E A2 + E Ag + Eg A+E A+E
F'g A+E B2 + E Bl + E B2 + E B, + E Bg + Eg B+E B+ E
Alu A Bl Bl A, Al Au B A
A 2u A Al A2 B, Bl Bu A B
Eu E Al + B l A, + Bl A, + B, Al + Bl Au + Bu A+B A+B
Flu A+E B, + E B 2 +E Al + E A, + E Au + Eu B+E B+E
F,u A+E A2 + E Al + E Bl + E B 2 +E Bu + Eu A+E B+E

* To find correlation~ with smaller subgroups, carry out the correlation in two steps; for
example, if the correlation of 0h with C2V is desired, use the table to pass from 0h to T d
and then employ the table for T d to go on to C2V .
246 Appendix 4

°h 3C, C" 2C~ C" Gh C" Gd

(cont.) D 2h D'h C'v C.v

A lg Ag Ag Al Al
A.g Ag Blg Al A,
Eg 2Ag Ag + Blg 2A l Al + A.
Flg Blg + B'g + Bag Blg + B.g + Bag A. + Bl + B. A. + Bl + B.
F.g Blg + B.g + Bag A lg + B.g + Bag A, + Bl + B. Al + Bl + B.
Alu Au Au A. A.
A.u Au B,u A. Al
Eu 2A u Au + Blu 2A. Al + A.
Flu Blu + B.u + Bau Blu + B.u + B3u Al + B l + B. Al + Bl + B.
F.u Blu + B.u + Bau Au + B.u + Bau Al + Bl + B. A. + B l + B.

°h C~, Gh 3C. C" 2C~ C" Gh C~, Gh

(cont.) C.v D. D. C. h C. h

Alg Al A A Ag Ag
A,g Bl A Bl Ag Bg
Eg Al + Bl 2A A + Bl 2Ag Ag + Bg
Flg A. + Bl + B. Bl + B. + Ba Bl + B. + Ba Ag + 2Bg Ag + 2Bg
F.g Al + A. + B. Bl + B. + Ba A+B.+B3 Ag + 2Bg 2Ag + Bg
Alu A, A A Au Au
A.u B. A Bl Au Bu
Eu A. + B. 2A A + Bl 2A u Au + Bu
Flu Al + Bl + B. Bl+B,+Ba Bl + B, + Ba Au + 2Bu Au + 2Bu
F.u Al + A. + Bl Bl + B. + B3 A+B.+Ba Au + 2Bu 2A u + B u

C. C'
°h Gh G,t
C,
•
C.
(cont.) Cs Cs Ci Cl

A lg A' A' A A Ag A
A.g A' A" A B Ag A
Eg 2A' A' +A" 2A A+B 2Ag 2A
Flg A' +A" A' + 2A" A +2B A + 2B 3Ag 3A
F.g A' +2A" 2A' +A" A +2B 2A +B 3Ag 3A
Alu A" A" A A Au A
A.u A" A' A B Au A
Eu 2A" A' +A" 2A A+B 2A u 2A
Flu 2A' +A" 2A' +A" A + 2B A +2B 3A u 3A
F.u 2A' +A" A' + 2A" A +2B 2A +B 3A u 3A
Correlation Tables 247

lh l C. Ca C. Cl

Ag A A A A A
Au A A A A A
Flg Fl A + El A+E A + 2B 3A
Flu Fl A + El A+E A + 2B 3A
F.g Fa A + Ea A+E A +2B 3A
F.u Fa A + E. A+E A +2B 3A
Glg Gl El + Ea 2A + E 2A + 2B 4A
Glu Gl El + Ea 2A +E 2A + 2B 4A
Hg H A+El+E. A +2E 3A + 2B 5A
Hu H A + El + E. A + 2E 3A + 2B 5A

REFERENCES
1. D. M. Adams, Metal-Ligand and Related Vibrations, St. Martin's Press, New York
(1968).
2. W. G. Fateley, F. R. DolIish, N. T. McDevitt, and F. F. Bentley, lnfrared and
Raman .Selection Rules for Molecular and Lattice Vibrations: The Correlation
Method, Wiley-Interscience, New York (1972).
 Appendix 5

ELEMENTARV MATHEMATICS

This appendix will attempt to present the fundamental definitions and theo-
rems necessary for an understanding of group theory. The presentation will
not be detailed, for the approach to group theory followed in this book
will be empirical rather than mathematical. For a more detailed discussion
of the subject see the texts by Margenau and Murphy(l) and others. (2-41

DEFINITION OF A GROUP

The group has been defined in Sectionl-4B. In summary,asetofelements

A, B, C, ... is said to be a group iffor every pair of elements (e.g., A and B)
a binary operation exists that yields the product AB which belongs to the
set; if the associative law holds for the combination of elements; if the set
contains the identity element; and if there is an inverse for each element.

FINITE AND IN FINITE GROUPS

Groups containing a limited number of elements are called finite,

while groups containing an unlimited number of elements are called infinite.
The number of elements, g, in a finite group determines the order of the
group. All of the groups that we will encounter will be finite groups of
order g, with the exception of those for linear molecules, of which there
are two (Coov , D ooh ).

SUBGROUPS

Inspection of a group will show that within the group there are smaller
groups with the same operation. In the group Cav , which is of order 6, the
following smaller groups will be found; E by itself; O'v' of order 2; and Ca,
of order 3. If the order of the group is g, then the order of the subgroup, h,
must be an integral divisor of g.

249
250 Appendix 5

CLASSES
If A and B are elements of a group, then B-lAB will be equal to some
element Y of the group. Thus
Y = B-lAB (A5-l)

Y is called the transform of A by B, or we say that A is conjugate to Y.

The following are properties of conjugate elements:
1) every element is a conjugate to itself;
2) if A is conjugate to Y, then Y is conjugate to A; e.g., A = B-l YB;
3) if A is conjugate to Yand Y is conjugate to X, then A is conjugate
to X and A, Y, and X belong to the same dass.

A complete set of elements conjugate to each other is called a dass of the

group.
The method of arranging the elements of a group into dasses exhibits
the structure under the relation of conjugation. The result is that the sym-
metry of the molecule can be presented as a set of disjoint sets of geometric
(symmetry) elements. For Cav the complete set of elements conjugate to
each other is E, Ca, C~; O"v1, O"v" O"v3. For C4V : E, C4 , Cf; C2 - C:; O"v1,
O"v.; O"d1, O"d'·

DEFINITION OF A MATRIX
A collection of real or complex quantities displayed in a table of rows
and columns is called an array. The most familiar type of array is the de-
terminant, which always has the same number of rows and columns, and
is always a number. It can be written as

An A l2 A 13 ••• A ln
A 2l A 22 A 23 . .. A 2n
A = IA I = A 3l A a2 A 33 . .. A 3n (A5-2)

A matrix, on the other hand, is an array in which the number of rows and
columns can differ. It is an element from a set of matrices with a specific
(row-by-column) multiplication (unlike determinants, which have different
multiplications in the sense that the determinant is a number and this
number is invariant under the interchange of rows and columns). The ma-
Elementary Mathematics 251

trix product is not a number. However, a matrix product can have a set of
determinants of various orders. We may represent a matrix as

Au Au A l3 ••• Alm
A 21 A 22 A 23 ... A 2m
A = [Ai,j] = A 31 A 32 A 33 ... A 3m (A5-3)

Here n and m determine the order of the matrix, n giving the number of
the rows and m the number of columns. When n = m, the matrix is called
square.

MULTIPLICATION OF MATRICES
A matrix A having three rows and three columns is to be multiplied by
a matrix B having three rows and two columns. The row elements of matrix
Aare multiplied by the corresponding column elements of B. The following
example will illustrate this operation:

Au Al2 AI~ BU Blj

A = [ A 21 A 22 A 23 B = [ B 21 B 22 (A5-4)
A 31 A a2 A a BaI Ba
(3 X 3 matrix) (3 X 2 matrix)

AUBll + A u B 21 + A 13B al A u B l2 + A l2B 22 + A laBa2]

= [ A 21 Bu + A 22B 21 + A 2a Bai A 2l B l2 + A 22B 22 + A 2aB32 = C (A5-5)
AalBu + A a2B21 + AaaBal AalBu + A a2B22 + A aaBa2
Thus, AB = C. Here the product is a matrix of three rows and two columns.

TRANSPOSE OF A MATRIX
Consider the matrix

(A5-6)
252 Appendix 5

Hs transpose is

(A5-7)

REPRESENTATION OF GROUPS
The elements of a group, such as the symmetry operations of a mole-
eule, can be represented by matrices. For true representations, the multi-
plication of the numbers representing A and B of the group must, if AB
= C, lead to the number which represents the element C. A set of numbers
or matrices which can be assigned to the elements of a group and which
can properly represent the multiplications of the elements of this group is
said to constitute a representation of the group. This can be illustrated by
considering the moleeule NH 3 in the C3V point group (Fig. A5-1). The fol-
lowing treatment is taken from an article by Ziomek. (2)

The following internal coordinates can be written:

LlD l change in bond distance XY1
LlD 2 change in bond distance XY2
LlD3 change in bond distance XY3
Lla12 change in angle Y1XY2
LI a 13 change in angle Y1XY3
Lla23 change in angle Y 2XY3

Z
I
I
I
I

Fig. A5-1. The NH 3 (XY3) molecule showing the x, y, z coordinates.

Elementary Mathematics 253

If the ct (1200 clockwise) symmetry operation is carried out for the XYa
molecule, the following shifts occur:

let
LlD l LI Da
LlD 2 LlD l
LI Da LlD 2 (A5-8)
Llal2 Llala
Llala Lla 23
Lla23 Lla12

If the resulting shifts are written for all the symmetry operations in the
Cav point group, the following table is obtained:

Cav I E ct Cä O'v1 O'v' O'v 3

LlD l LlD l LI Da LlD 2 LlD l LlD3 LlD 2
LlD 2 LlD2 LlD l LI Da LlD3 LlD 2 LlD l
LlD 3 LlD3 LlD 2 LlD l LlD 2 LlD l LlD 3 (A5-9)
Llal2 Llal2 Llala Lla 23 Llal3 Lla 23 Lla 12
Llal 3 Lla 13 Lla23 Llal2 Lla12 Llal3 Lla23
Lla23 Lla 23 Llal2 Llala Lla23 Llal2 Lla l3

Each column can be considered a vector. If we take column ct,

the vector
rat whose components are given under ct is a transform ofthe vector whose
components are under c 3v . Symbolically rat = D(Ct)r, where D(Ct)
is a matrix used to transform r into rat' and in more detail this becomes

LlD 3 001 000 LlD l

LlD l 100 0 0 0 LlD 2
LlD 2 o1 0 0 0 0 LlD3
(A5-1O)
Llal3 o0 0 0 1 0 Lla12
Lla23 o 000 0 1 Llal3
Lla12 000 1 0 0 Lla 23

This procedure can be repeated for each of the symmetry operations. A

set of 6 x 6 matrices that is a group is obtained, and it is a six-dimensional
representation. This set is displayed below in such a way that the element
R of the group is given first, its corresponding D(R) second, the sum X(R)
of the terms along the diagonal (called trace) third, and the value of X(R)
last:
254 Appendix 5

1000 00
o10 0 0 0
001 000
E~ -D(E) x(E) = 6 (A5-11)
000 1 0 0
000 0 1 0
00000 1

001 000
10 0 00 0
o10 00 0
= D(C:)
C:~ x(C:) = 0 (A5-12)
000 0 10
o0 0 0 0 1
000 10 0

o 1 0 000
o 0 1 000
100 0 0 0
C3~
o0 0 0 01
== D(Cä) x(Cä) = 0 (A5-13)
000 1 0 0
000 0 1 0

100 0 0 0
o 0 1 000
o 1 000 0
O'v1 ~
o 0 0 0 1 0 == D(O'v 1) x(O'vl) = 2 (A5-14)
000 1 0 0
00000 1

o 0 1 000
o10 0 0 0
100 0 0 0
O'v2 ~
o0 0 0 0 1 == D(O'v2) x(O'v2) = 2 (A5-15)
o0 0 0 10
000 1 Ö0

o10 0 0 0
100 00 0
o0 1 000
1 0 0 = D(O'v·) x(O'v.) = 2
O'v· ~ (A5-16)
000
o0 0 0 0 1
o0 0 0 10
Elementary Mathematics 255

The matrices given in (A5-11) to (A5-l6) are ofa special form when they are
partitioned as 2 X 2 matrices. For example,

001 II 000
100 I 000
010:000
c;t -+ - - - -1- - --
000 010
~[~ ~] (A5-l7)

000 001
000 100
where

A = [0100
01] 0 0 0]
0= [ 000 C = [0001
10] (A5-l8)
010 000 100

Here the matrix representing C3 + is said to be in the reducible form. If

a set of matrices can be presented in this form, it, too, is said to be in the
reducible form. Since the set of matrices in (A5-11) to (A5-l6) is called
a representation and since its matrices can be presented in reduced form,
the representation is reducible. This statement implies that a transforma-
tion (called similarity) can be employed on the original set to display the
matrices in the reduced form. The representation (set of matrices) so
treated is called a reducible representation. If no similarity transformation
exists, the representation is said to be irreducible
Another criterion is the following. If

~ 1 x(R) 12 > g (A5-l9)

R

the representation is reducible, and if

~ 1 x(R) 1
2 = g (A5-20)
R

the representation is irreducible.

The trace of the 6 x6 matrices of Eqs. (A5-11) to (A5-l6) is the sum
of the diagonal terms. Thus, the traces for the transformations of the dis-
placement coordinates are

The set of traces is called the character of the representation. It may be

summarized as folIows:
256 Appendix 5

vib (NH a) 6 0 0 2 2 2 (A5-21)

L I X(R)2 = 62 +2 +2 +2
2 2 2 = 48
R

Since 48 > 6, where g = 6 (the number of elements in a Cav group), the

representation is reducible. This reducible representation can be decomposed
into a sum of irreducible representations. For the purpose of decomposition
the characters of the irreducible representations are required. These charac-
ters are conveniently given in tabular form, the character table for C3V ,
for instance, being written as folIows:

C av E 2Ca 3av

Al XAl(E) XAl(Ca) XAl(aV )

A. XAa(E) XA2(Ca) XA.(a v)

E XE(E) XE(Ca) XE (I1v)

Since, from the character table for C3V ,

2XA/E) 2XAJCa) 2XA l (O'V) 2 2 2

2XE(E) 2XE(C3 ) 2XE(O'V) 4 -20
add
2XA l (E)+2XE(E) 2XA l (C3 )+2XE(C3 ) 2XA l (O'V) + 2XE(O'v) 6 o2
we may write

PROBLEMS

l. Multiply the following matrices:

a) [H~] X [1]
b) [~] X [D E Al
 n
Elementary Mathematics 257

c)
[4 56] x [
d)
U] x [456]
e)
[1 2 3] x
[40 -6
-7
96 6]7

n
5 8 -11 -8
f)
[~;:] x [
g)
[1 21] x [3
402
-4]
_~ ~
h)
[AD EB C]
F x [J
LMK]
G H I NO

[A B C] [J K]
i)

D E F x t~

Answers

a)
[AJ+BK+CL]
DI+EK+FL
GI +HK+IL
b)
[AD + AE + AK]
BD+BE+BK
CD+CE+CK
c) [29]

d)
[ 128 1015 12]
18
-4 -5 -6
e) [19 4 -12 -4]
f)
[~~]
258 Appendix 5

g)
[~ -1~]
h) [Al + BL + CN AK+ BM + CO]
Dl + EL + FN DK+ EM + FO
Gl + HL + IN GK+ HM + 10
[Al + BL + CN BM + CO]
i) AK+
Dl + EL + FN DK+ EM + FO

REFERENCES

1. H. Margenau and G. M. Murphy, The Mathematics oJ Physics and Chemistry, D. Van

Nostrand Co., Ine., New York (1956).
2. J. S. Ziomek, "Group Theory" in: Progress in InJrared Spectroscopy, Vol. 1 (H. A.
Szymanski, ed.) Plenum Press, New York (1962).
3. F. A. Cotton, Chemical Applications oJ Group Theory, Interscienee Publishers, New
York (1963).
4. G. Stephenson, Mathematical Methods Jor Science Students, Longmans, London
(1962).
 Appendix 6

THE gELEMENTS

It has been mentioned in Chapter 4 that the element~ of the g matrix

are. given in terms of the internal coordinates, the bond stretching, r, and
the angle deformation, rp. Wilson, Decius, and Cross(l) have suggested a
method by which the gelements can be described. Figure A6-1 shows the
schematic representations of the g elements. The superscript always in-
dicates the number of common atoms. Atoms common to both coordinates
are indicated by double circles, and are always put in a horizontalline. The
noncommon atoms are indicated along a 45° diagonal. When a single com-

Table A6-1. g Elements-General Case

g:. "'1 + "'2

g~ "'1 COS 'P
g~tp - (lIS"'Z sin 'P
g~"m (lU"'l sin 'P cos T
<D - «(lu sin 'Pm cos '1'834 + (l14 sin 'PZ14 cos 'l'24S)"'1
g;CP (l~Z"'1+ (l:a"'s + «(l~2 + (l:s - 2(lU(l83 COS 'P)"'2
g:,,<D «(l~2 COS 'l'S14)"'l + [«(lu - (l2S COS 'PUS - (lu cos 'PU4)(lu COS 'l'S14
+ sin 'P12S sin 'PU4 sin8 'l'S14 + COS 'PSZ4 cos 'l'314)(l2S(lZ4]"'Z
m -(lu cos T[«(lu - (l14 COS 'Pl)"'l + «(lu - (las cos 'Pz)"'z]

g:'I'<:) - sin TZ5 sin TM + COS Tu COS Ta4 COS 'Pl)(lU(l14"'1

m (sin!pm cos 'Pm COS TM - sin 'PZ15 COS Ta.)(l14
. 'PZ15 COS 'Pu. COS TS5 - sm
+ sm ' ) (ln"'l
'P.14 COS TS4 (l15 - . - -
sm'PUS
[(COS 'PU5 - COS 'PS14 COS 815 - COS 'P.14 COS 'PilS + cos 'PalS COS 'PZ14 COS 'Pan)
X (l12(l13 + (cos 'PUS - COS 'P514 COS 'Pö13 - COS 'P.14 COS 'PZlS
+ COS 'PilS COS 'PZ14 COS 'P51S)(l12(l15 + COS 'Pm - COS 'Pan COS 'Pa15
- cos 'Pu. COS 'Pu. + COS 'Pua COS 'Pus COS 'Pa15)(l14(l13
+~~-~~~~-~~~~+~~~~~~

X (l14(l1.] - , - -"'1
----
sin 'PZ14 sin 'P815

259
260 Appendix 6

2
9rr ~ g~q> ~

I
grr

:>
g~CP(1)

>
g~'P~
g~CP (6)
~
g~CP (~)

~
~
Fig. A6-1. Schematic representations of gelements for nonlinear molecules. [From
Molecular Vibrations by E. B. Wilson, J. C. Decius, and P. C. Cross, McGraw-Hill,
New York (1955), as modified in Introduction to Infrared and Raman Spectroscopy by
N. B. Colthup, L. H. Daly, and S. E. Wiberley, Academic Press, New York (1975).
Used by permission of McGraw-Hill Book Company and Academic Press.]
The gEIements 261

Table A6-2. gEIements for ffJ = 109°28'

g:. ftl + ft.

g;" -tftl
g~CP - i V2e'3ft.
g~CP<D iV2e13ftl cos,
g~,/D t V2(e13 + (14)ftl
g:cp e~.ftl + e:3ft3 + t(3e~. + 3ef3 + 2eUe.3)ft.

g:cp<D -t{ 3e:lftl + [3e:1 + (e .. + e•• )e21 - 5e.3e •• 1ft.}

g:'I'cn -teu cos ,[(3eu + (14)ftl + (3eu + e.3)ft.1
g~'I'm -!(3 sin "5 sin '3. - COS "5 COS '3.)eUeuftl
g~cp(D -H(3 cos '35 + COS '3.)eU + (3 COS '34 + cos '35)e151Quftl
g~/D -i(eu.+ eU)(Q13 + (15)ftl

mon atom is the terminal atom in a bending vibration, the notation g;'I'(D
is used; when it is the central atom in a bending vibration, the notation
glcp<D is used. Here, the pair of numbers in parentheses has the following
significance: the top number gives the number of atoms in the top left
line, and the bottom number gives the number of atoms in the bottom left
line of the schematic representation. Tables A6-1 to A6-3 record the g
elements for the general case, the case where rp = 109°28', and tbe case

Table A6-3. gEIements for ffJ = 120°

ftl + ft.
g;" -tftl
g~CP - t f ie•3ft•

g~'I'm tfiel3ftl cos,

g~'I'<D tfi(e13 + (14)ftl
g;CP e~.ftl + e~3P3 + (e~. + e:3 + eUe.3)p.

g:'I'<D -H2e~,PI + [e12(2eu + e.3 + e•• ) - e.3e •• 1p.}

g:'I'(D - tel. cos ,[ (2Qu + eU)PI + (2el' + Q.3)p.1

g~cpm -Hcos "5 COS '3. - 2 sin "5 sin '3.)eUeUPI
g~'I'm t cos '3. (eu - eI5)e12ftl
g~/D This type of g element impossible when ffJ = 120°
262 Appendix 6

g3
cpcp
~
3 2
g2 (Ö)~
CPcP 3 2 4

gl (2)
cpcp2 ~
3 2 4 5
Fig. A6-2. Schematic representations of g
elements for linear molecules.

where rp = 120°. For results inc1uding torsions, out-of-plane bending, and

cyc1ic structures, see Decius. (2) Ferigle and Meister(3) have determined
formulas for gelements for linear cases, and these are illustrated in
Fig. A6-2.
For the use of the formulas in Tables A6-1 and A6-3, it is necessary
to define certain terms; f-l and e are the reciprocals of mass and bond
distance, respectively. The formulas also involve an angle 1p, which is defined
as

ß
~a8ß~~ß8Y
a~Y
'Paay
I

2'3~,.
4

Fig. A6-3. Definitions of notation used in Appendix 6.

The gEIements 263

the notation being defined by the top diagram in Fig. A6-3. The torsion
angle T is defined by the two bottom diagrams in Fig. A6-3.

REFERENCES
1. E. B. Wilson, J. C. Decius, and P. C. Cross, Molecular Vibrations, McGraw-Hill,
New York (1955).
2. J. C. Decius, J. Chern. Phys., 16: 1025 (1948).
3. S. M. Ferigle and A. G. Meister, J. Chern. Phys., 19: 982 (1951).
 Appendix 7

GENERAL METHOD OF OBTAINING

MOLECULAR SYMMETRY COORDINATES

A general method for obtaining molecular symmetry coordinates has been

developed by Nielsen and Berryman. (1) According to them, the prescription
for determining symmetry coordinates is given as follows.
1. Choose a linear combination L k of the internal coordinates from a
set of equivalent coordinates.
2. Then the sum
(A7-1)

will be a symmetry co ordinate belonging to the ath row of the irreducible

representation Dj and its lj - 1 partners will be given by

(A7-2)

Here the subscript k labels the number of symmetry coordinates in the jth
irreducible representations, Dj(R)a.a. and Dj(R)ßa. are matrix elements from
the ath row and ath column and from the ßth row and ath column of the
matrix Dj(R) for the jth representation, respectively, R represents an element
of the group, and RLk represents the transform of L k by R. The order of the
molecular symmetry group is ~.
Consider the moleeule XY a (NH 3), whose symmetry is given by C3V •
Figure 7-1 illustrates the geometrie configuration and the set of internal coor-
dinates chosen. According to their prescription, one requires the matrix
elements for the irreducible representations of Cav , the chosen set of inter-
nal coordinates, the transforms of the internal coordinates to form tbe
transforms ofthe linear combinations ofinternal coordinates, the dimensions
ofthe irreducible representations, and the order ofthe group. First, the cho-
sen set of internal coordinates is Lldl , Lld2, Lld3 , Llal2' Llal3' and Lla23.

265
266 Appendix 7

I
,----------------

Fig. A7-1.

Second, the following table gives the transforms of these internal coordi-
nates:

rk Rlrk R.rk R 3 r lc R.rlc R 5 Yk R 6 rlc R

-- ---
c 3V E c+3 c-3 a Vl av• a V3
---
.dd, .dd, .dd3 .dd• .dd, .dd3 .dd• Yk Rrlc
.dd. .dd2 .dd, .dd3 .dd3 .dd. .dd,
.dd3 .dd3 .dd• .dd, .dd2 .dd, .dd3
.da12 .da l2 .dal3 .da' 3 .da l3 .da' 3 .dal •
.da' 3 .da23 .da12 .dal3 .da' 3 .da l • .dal3
.dal3 .dal3 .da' 3 .dal • .dal2 .da l3 .da' 3

where the legend is

R

where rk is the kth internal coordinate and Rrk is the transform of rk by R.

Third, the se1ection rules state that there are two fundamental modes of mo-
tion in the Al and two in the E irreducible representations. This implies
that k will take on values 1 and 2 in Al species and 1 and 2 in E species.
Therefore for s~" for Al one has St,.l and stocl ; and for S~" for E one has
(Sfcc, S~) and (S~, S~). Fourth, the matrices for the irreducible represen-
tation of C 3V are given by the table
General Method of Obtaining Molecular Symmetry Coordinates 267

R, R2 R3 R. Rs R.

j DJ(R,) DJ(R 2 ) DJ(R 3 ) DJ(R 4 ) DJ(R s ) DJ(R.)

E C+
a c-a aVI aV2 aV3

A,
A2 -1 -1 -1

E (~ 0)1(-t
-!v'3
tv'3) ( -! tv'3)
-! !v'3 -!
C
0 -10) (-t
-tv'3
-!v'3) (-t_ ;!v'3)
t tv'3

For the Al representation first choose

and
Then
S!i' = tLR DA ' (R)l1 RL l

Sd ' = t[DAI(E)l1ELl + DA'(Ct)CtLl + D A1(Cil)CiL l

+ DAI(av)aVILl + DAI(av.)av.Ll + DAI(ava)avaLd
= t(1 L1d + 1 L1d + 1 L1d + 1 L1d + 1 L1d + 1 L1d
l 3 2 l 3 2)

= t(L1d + L1d + Lld

l 2 3)

Thus S~l = tCL1dl + L1d + L1d 2 3) and one then chooses

as one of the normalized symmetry coordinates of Al type. There is no part-

ner to this co ordinate since the Al representation is nondegenerate and hence
one dimensional.
In a similar manner one obtains

S1 ' = t L DA ' (R)Ra l2 = t(L1a l2 + L1a13 + L1a 23 )

R

and then the choice is

268 Appendix 7

For the E species one has (Sfl' SiD and (S~, S~). First consider LI = LId,
11 = 2, and h = 6. Then

S~ = i[DE(E)nLl + DE(Ct)nLl + DE(C"i)L 1

+ DE(av)L 1 + DE(aV2 )L1 + DE(O'va)L 1]
= tel Lld
1 -t Lld t Lld + 1 Lld 1 Lld
3 - 2 1 - 3 - t Lld2 )
S~ = te2 Lld1 - Lld2 - Lld3 )

Normalized, we have

The first and only partner of S~ is Sf2 and is obtained from the following
expression:

which becomes

S~ = i[DE(E)21ES~ + DE(Ct)21CtS[i + DE(C"i)21C"iS~

+ DE(aVJ)aV1S~ + DE(aV2)aV2S~ + DE(ava)avaS~]
= 30(Lld 2 - Lld3 )

Then S~ is taken to be

Hence the normalized and orthogonal pair selected for the first set of de-
generate symmetry coordinates is

S:;' = (1/0)(2 Lld1 - Lld2 - LIds)

S~ = (1/V2)(Lld2 - LIds)

For (S~, S~) one takes L 2 = Aa12 and k = 2, and

S~ = t L DE(R)nRL 2
R

becomes
General Method of Obtaining Molecular Symmetry Coordinates 269

while
S22
E -- ~6 ,--
L.,
DJt(R) 21 RS21
E
R

becomes

Then for (S~, S~) to be symmetry coordinates one chooses the following
orthogonal and normalized pair:

s~ = (l/V6)(Lla12 + Lla 13 - 2 Ll( 23 )

S~ = (l/V2)(Lla12 - il(13)

REFERENCE

I. J. R. Nielsen and L. H. Berryman, J. ehern. Phys., 17:659 (1949).

 Appendix 8

CALCULATION OF THERMODYNAMIC
FUNCTIONS FROM VIBRATIONAL-
ROTATIONAL SPECTRA

From the vibrational-rotational spectra of a moleeule, it is possible to

determine the thermodynamic functions of the moleeule. Abrief discussion
folIows. For a more detailed discussion, see the books by Herzberg(l) or
Glasstone. (2)
It can be shown that~he total energy in a moleeule i8 the sum of the
translational energy and the internal energy, where the internal energy is
the sum of the vibrational, rotational, and electronic energies.

E tota1 = Etr + Eint (A8-I)

Eint = E Yib + Erot + E e1ec (A8-2)

therefore,
E tota1 = E tr + E Yib + Erot + E e1ec (A8-3)

The total energy of a moleeule is found to be related to the partition function

Q as folIows:
(A8-4)

where gi is the total statistical weight (degeneracy), k is the Boltzmann

constant, and T the absolute temperature, Therefore

(A8-5)

and Qelec i8 usually neglected since it is very smalI. Qtotal is related to all the
thermodynamic functions as folIows.
Enthalpy or heat content, (HO)

HO - Eo = RT d In Qtot +R (A8-6)
T dT

271
272 Appendix 8

where R the molar gas constant, equal to 1.987 cal/deg . mole, and E o
is the total energy at absolute zero for one mole of an ideal gas.
Heat capacity at constant volume (C~)

c~ = :2 [d2Qto~:~1/T)2 - ( dQto~:~l/T) fJ (A8-7)

Entropy (SO)

SO = RT d In
dT
Qtot + R In Q tot - R In N +R (A8-8)

where N is the number of distinguishable particles in agas, and can be

assumed to be the number of moleeules in a mole, or Avogadro's number.
Free energy (GO)

GO - E o = _R In Qtot (A8-9)
T N
Qtot is reiated to the other Q's as in Eq. (A8-5). Since Qrot and
Qvib can be
related to spectroscopic data, it follows that thermodynamic functions can
be obtained from spectroscopic data. For example, for a linear moleeule,

Q _ 8nHkT
rot - ah 2 (A8-IO)

where a is the symmetry number and is equal to the number of equivalent

orientations of the moleeule which can be obtained by rotation, h is Planck's
constant, and I is the moment of inertia. The value of I can be obtained from
the equation
h
I = -'4:-n-::2c-Ll-'v- (A8-11)

where Llv is the spacing between absorptions in the rotation al fine structure
of the moleeule, and cis the velocity of light (2.9978 x 1010 ern/sec). Thus,
the Qrot contribution to aII the thermodynamic functions can be determined
from spectroscopic data. For the Qvib contributions, assuming a harmonie
osciIIator and no coupling between rotation and vibration,

1
Q vib -- e-hvc/2kT -,-----;,---,-;-=-
1 _ e-hvc/ kT (A8-12)

where v is the frequency in cm-1 and Qvib can be determined for each fun-
Thermodynamic Functions from Vibrational-Rotational Spectra 273

damental frequency (v) and summed. The Qvib contribution to each ther-
modynamic function can then also be determined. The Qtr contribution
can be calculated from known formulas and added to the rotational and
vibrational contributions. The thermodynamic functions are thus determined
as functions of the temperature.

REFERENCES
1. G. Herzberg, Molecular Spectra and Molecular Structure, II, Infrared and Raman
Spectra of Polyatomic Molecules, Van Nostrand, New York (1945).
2. S. Glasstone, Theoretical Chemistry, Van Nostrand, New York (1944).
 Appendix 9

DIAGRAMS OF NORMAL VIBRATIONS

FOR COMMON POINT GROUPS

Normal modes of vibration of bent ABI molecule-point group C1W •

A 8 C
o ~ E 0 E 0

o )' o ~ ( 0

Normal modes of vibration of linear ABC molecule-point group Cootl •

8 A
0 0-+ 111

t ; V2. }
o 0 0
1I2b
+

o ,.
( " 1I3
Normal modes of vibration of linear A8 or ABA molecule-point group Dooh •

275
276 Appendix 9

Normal modes of vibration of pyramidal AB a molecule-point group Ca.-

Normal modes of vibration of planar AB s molecule-point group DSh -

1I2(E)

Normal modes of vibration of tetrahedral AB, molecule-point group Ttl -

Diagrams of Normal Vibrations for Common Point Groups 277

I
I
I
I
I
I
I

BI V-------

Normal modes of vibrations of square planar AB. molecule-point group D.ho

Normal modes of vibrations of pyramidal AB. molecule-point group C,vo

278 Appendix 9

+,'" +,'"
,
0::____ ___, _ _____ _,
."

r+' "
'- --
,
---'

Zl6(E')

Normal modes of vibrations of trigonal bipyramidal AB. molecule-point group D 3 ,.-

Normal modes of vibrations of octahedral AB s molecule-point group 0,,_

 Appendix 10

DERIVATION OF THE CHARACTERS

NECESSARY FOR SELECTION RULES

In the development of selection rules for isolated molecules (see Chapter 2),
it is necessary to derive the character of the dipole moment to be used in
determining the infrared activity, the character to represent the polarizability
for the determination of Raman activity, and the character to determine the
number of fundamentals belonging to each vibration type. The derivation
of these characters follows.

DERIVATION OF THE CHARACTER OF THE DIPOLE

MOMENT XM{R)

Consider a co ordinate system (x, y, z) and assume a molecule whose

center of gravity is located at p (Fig. AlO-l). If one performs a proper op-
eration along the z axis such as a clockwise rotation of angle e(C(;\;), x is
displaced from the equilibrium position to x', y is displaced to y', and z
remains invariant. The relationships between x and x', y and y', and z
and z' are
x' = x cos e + y sin e
y' = -xsin e + ycos e (AlO-l)
z' = z

In matrix notation this becomes

X' ]
[:: [X] [COS e sin e 0] [X]
= C(;\; ~ = -~in e ~os e .~ ~ (AlO-2)

The character of the matrix is the sum of the elements along the diagonals
(also called the trace or spur) and is given by

XM(R) = XM(C(;\;) = (1 + 2 cos e) (AlO-3)

279
 280 Appendix 10

z z

;----y

x x
Fig. AIO-l.

The same results are obtained if the rotation operation is performed coun-
terclockwise (Ce). Equation (AlO-3) can be written for the general case
as follows:
(AlO-4)

where flR is the number of atoms left unchanged by the operation.

If one considers an improper operation such as a rotation-refiection
(S), the x, y coordinates are again displaced to x', y' but in this operation
the z co ordinate also changes (Fig. AIO-2). The relationships between the
equilibrium positions and the dis placements can now be written

x' = x cos e + y sin e

y' = - x sin e + y cos e (AlO-5)
z' =-z

z z

----4.. --
Cf"xy
J-----y ",,~-----y

/.
, ... / -_
-y I

,/
x/
x x
z'
Fig. AIO-2.
Derivation of the Characters Necessary for Selection Rules 281

Written in matrix notation, the expressions beeome

(AI0-6)

The eharaeters beeome

XM(R) = XM(S) = (-1 + 2 eos (9) (AlO-7)

For the general ease the eharaeter is written

XM(R) = flR( -1 + 2 eos (9) (AI0-8)

Thus the eharaeter for the dipole moment neeessary to ealculate the in-
frared aetivity is
(AI0-9)

where the plus sign is used for proper operations and the minus sign for im-
proper operations.

DERIVATION OF THE CHARACTER OF THE

PO LARIZABI LlTY X,,(R)

For most molecules the polarizability a may be different in the x, y,

and z direetions. For the general ease the following equations apply:

fix = axxEx + ayxEy + axzEz

fly = ayxEx + ayyEy + ayzEz (AlO-lO)
flz = azxEx + azyEy + azzEz

where E represents a veetor of the eleetronie field and fl is the indueed di-
pole moment. Sinee the polarizability tensor is symmetrie, a xy = a yx '
a yz = a zy ' and a xz = a zx . Thus, there are six eomponents to the symmetrie
tensor of polarizability. If a partieular operation sueh as Ca is performed,
the eomponents of polarizability will undergo the following ehanges:
282 Appendix 10

The relationships between the equilibrium polarizabilities and the ehanged

polarizabilities are given in matrix notation as follows:

CXIXCYIXCZIX]
[ CX'yCY'yCz,y (AlO-ll)
CX,zCy,zCz,z
A B

where CXI X denote the direetion eosine between the axes Xl and X, ete. (Note
Bis the transpose of A.) For a rotation (proper operation) through an an-
gle f), the relationship beeomes

-sin f) 0]
eos f) 0
o 1
(AIO-12)
whieh ean be written

a XX
a yy
a zz
Ce
a xy
a xz
a yz_
eos 2 f) sin 2 f) 0 2 sin f) eos f) 0 0
sin 2 f) eos 2 g 0 -2 sin g eos f) 0 0
0 0 0 0 0
-sin f) eos f) sin g eos g 0 2 eos 2 f) - 1 0 0
0 0 0 0 eos f) sin f)
0 0 0 0 -sin f) eos f)

a XX
a yy
a zz
X (AIO-13
a xy
a yz
a yz_

The eharaeter of this representation is

(AIO-14)
Derivation of the Characters Necessary for Selection Rules 283

Since
cos 2(9 = 2 cos 2 (9 - 1

and
tecos 2(9 + 1) = cos 2(9

substituting in Eq. (AIO-14), one obtains

X",(C e ) = 2 + 2 cos (9 + 2 cos 2(9 (AlO-15)

For an improper operation

X",(S) = 2 - 2 cos (9 + 2 cos 2(9 (AlO-16)

Thus, for proper and improper operations one obtains the character

X",(R) = 2 ± 2 cos (9 + 2 cos 2(9 (AlO-17)

This is the character to be used for the determination of the Raman activity.

DERIVATION OF THE CHARACTER FOR THE

DETERMINATION OF NUMBER OF
FUNDAMENTALS XE: (R)

The character previous1y developed for the dipole moment refers to 3n

variables, where n is the number of atoms in the molecule. For characters
applying to representations for 3n - 6 coordinates, the characters for the
motions of translation and rotation must be subtracted.
The n vectors giving the displacements of the nuclei are, by the laws
of mechanics, equivalent to the resultant vector acting at the center of
gravity of a molecule. The three components of this vector transform for
the translation like that of the dipole moment. Therefore
(AlO-18)

For displacements involving rotation one must consider angular momentum

changes for each coordinate. For a proper rotation such as a rotation about
the z axis (Ce), the changes are represented by
Ix' = Ix cos (9 + Iy sin (9
ly' = -Ix sin (9 + Iy cos (9 (AlO-19)
Iz' = lz
284 Appendix 10

For an improper operation S

Is" = -Ix cos (9 - Iy sin (9
Iy" = Ix sin (9 - Iy cos (9 (AlO-20)
Iz" = Iz

Therefore XR(R) = 1 + 2 cos (9 for the Ce operation, and XR(R) = 1 - 2

cos (9 for the S operation, and for 3n - 6 coordinates the character for the
number of fundamentals XB(R) be comes
(A 10-2 1)

For a proper operation (Ce)

XB(C e ) = .uR(l + 2 cos (9) - (1 + 2 cos (9) - (1 + 2 cos (9) (AlO-22)
XB(C e ) = .uR(l + 2 cos (9) - 2(1 + 2 cos (9)
XB(C e ) = (.uR - 2)(1 + 2 cos (9) (AlO-23)

For an improper operation (S)

XE(S) = .uR[( -1 + 2cos (9) - (-I + 2 cos (9) - (1 - 2 cos (9)] (AlO-24)
(AlO-25)

REFERENCE

J. E. Rosenthai and G. M. Murphy, Rev. Mod. Phys., 8:317 (1936).

 Appendix 11

UPDATED BIBLIOGRAPHY

In the time elapsed since the submission of the manuscript for this edition,
many publications relevant to the subject matter have appeared in the open
literature. The most important of these are Iisted below.

1. J. D. H. Donnay and G. TUfrell, Chem. Phys. 6:1 (1974).

2. G. TUffelI, Infrared and Raman Spectra of Crystals, Academic Press, London (1972).
3. L. L. Boyle, Spec. Acta, 28A:I347 (1972).
4. L. L. Boyle, Acta Cryst. 28A:I72 (1972).
5. L. L. Boyle, Spec. Acta, 28A:1355 (1972).
6. C. Hsu and M. Orchin, J. Chem. Ed. 51:725 (1974).
7. G. Davidson, Introductory Group Theory for Chemists, Elsevier, London (1971).
8. S. D. Ross, Inorganic Infrared and Raman Spectra, McGraw-Hill, New York (1972).
9. R. L. Carter, J. Chem. Ed. 48:297 (1971).
10. W. L. Jolly, The Synthesis and Characterization of lnorganic Compollnds, Prentice-Hall,
Englewood Cliffs, N.J. (1970).
11. D. Steele, The Theory of Vibrational Spectroscopy, W. B. Saunders, Philadelphia (1971).
12. M. St. C. Flett, The Theoretical Basis of Infrared Spectroscopy, in An lntrodllction of
Organic Compounds, F. Schein mann (ed.), Vol. I, Pergamon Press, Oxford (1970).
13. K. N. Rao and C. W. Mathews (eds.), Moleclilar Spectroscopy-Modern Research,
Academic Press, New Y ork (1972).
14. J. A. Salthouse and M. J. Ware, Point Group Character Tables and Related Data,
Cambridge University Press, London (1972).
15. G. W. Chantry, Slibmillimetre Spectroscopy, Academic Press, London (1971).
16. P. M. A. Sherwood, Vibrational Spectroscopy of Solids, Cambridge University Press,
London (1972).
17. V. C. Farmer, "Site Group to Factor Group Correlation Tables" and "Symmetry
and Crystal Vibrations," in The lnlrared Spectra 01 Minerals, The Mineralogical
Society, London (1974), pp. 515-525, 51-67.
18. D. F. Irish and M. H. Brooker, Appl. Spec., 27:395 (1973).
19. W. G. Fateley, Appl. Spec., 27:305 (1973).
20. J. R. Ferraro, Appl. Spec., 29:354, 418 (1975).
21. D. M. Adams, Coord. Chern. Rev., 10: 183 (1973).
22. C. F. Shaw and L. G. Newbury, Can. J. Spec., 20:65 (1975).
22. M. H. Brooker, Appl. Spec., 29: 528 (1975).

285
 INDEX

ADAMS, D. M., 106, 108, 109,235,285 Calculations (Cant.)

ALPERT, N. L., 32 thermodynamic functions, 271
ANTOIN, D. J., 100 CARTER, R. L., 285
Centered lattice, 30
BAGLIN. F. G., 100 CHANTRY, G. W., 285
BARROW, G. M., 32 Character tables, 18
BASILE, L. J., 179 definition, 18
BAUER, S. H., 199 representation, 19
BEGUN, G. H., 186, 187, 194, 199 linear molecules, 20
BELL, J. W., 109 nonlinear molecu1es, 19
BENTLEY, F. F., 83, 109,247 types
BERRYMAN, L. H., 265, 269 C s , Ci and C n groups, 201
BERTIE, J. E., 109 ~,~,~,~,~,~,~,W~
BHAGAVANTAM, S., 58, 108 203
Bhagavantam and Venkatearayudu C nv groups, 203
Method, 58,75, 77 C 2v , C sv , C 4v , C 5v , C 6v , 201-204
BOYLE, L. L., 285 C nh groups, 205
BRADLEY, C. A., 132 C 2h , C Sh , C 4h , C 5h , C 6h , 204-20
BRAGEN, J., 108 D n groups, 206
BRINKLEY, S. R., 180 D 2 , D s , D 4 , D 5 , D 6 , 206-208
BRINTZINGER, H., 179 D nh groups, 208
BROADLEY, J. J., 199 D 2h , D Sh , D 4h , D 5h , D 6h , 208-211
BROOKER, M. H., 108,225,233,285 D nd groups, 208
BURKE, T. G., 198 D 2d , D Sd , D 4d , D 5d , D 6d , 212-214
Sn groups, 215
Calculations S4, S6 , SB, 215-216
combinations or difference tones, 38 Cubic groups, 217
Coov ,54 T, Th , Td , 0, 0h, 217-220
T d ,33 C oov and D ooh groups, 221
fundamenta!s Coov ,221
Coov ,53 D ooh ,222
Td ,36 CHERNICK, C. L., 199
infrared modes CLAASSEN, H., 165,179, 180, 198, 199
Coov ,54 CLASE, H. J., 186, 187, 199
Td ,39 CLEVELAND, F. F., 33, 56, 108, 137, 165,
overtones 179, 180
Coov ,55 COLTHUP, N. B., 32, 165, 179
Td ,40 Comparison of BV and HH Methods, 75
Raman modes Coordinates
Coov ,54 interna!, 135, 151, 156, 157
Td ,39 norma!ization, 136, 139, 151, 157

287
288 Index

Coordinates (Cant.) DICKINSON, R. G., 108

orthogonalization, 136, 140, 151, 157 Dipole moment component, 201
redundant, 158 JJ-x, /J-y, /Lz, 201
symmetry, 135, 151, 157 DODD, R. E., 199
calculation, 265-269 DOLLISH, F. R., 83, 109,247
transformation, 141, 152 DONNAY, J. D. H., 285
Correlation method, 108 DUNCAN, A. B. F., 197
Correlation tables, 235 DURIG, J. R., 100, 108
C 4 , C 6 , D 2 , D 3 , D 4 , D 5 , D 6 , 235
C2v , C3v , C 4v , C5v , C 6v , C2h , C3h , 236 EDGELL, W. F., 197
C4h , C5h , C6h , D 2h , 237 Examples of H-H method, 77
D 3h , D 4h , 238
D 4h , D 5h , D 6h , 239 Factor group, 30
D 6h ,240 FANO, L., 198
D 6h , D 7h , C 7v , D 2d , D 3d , 241 FARMER, V. C., 285
D 4d , D 5d , D 6d , 242 FATELEY, W. G., 83, 109,235,247,285
D 6d , S4, S6 , Sg , T, , T h , 243 FERIGLE, S. M., 56, 108, 179,262,263
0, 0h, 243 FERRARO, J. R., 32, 109, 179,285
Oh,246 FLETCHER, W. H., 199
I h ,247 FLETT, M. St. C., 285
COSTA, G., 180 FORNERIS, R., 179
COTTON, F. A., 32, 199,258 FREEMAN, S. K., 32
COUTURE, L., 225, 233
CRAWFORD, B. E., 180 GALLASSO, V., 180
CROSS, P. C., 132, 173, 179, 259, 260, GAUNT, J., 179, 197
263 g elements, 259
Crystallographic symbolism, 223 for <p = 10'1'28', 261
for <p = 12<Y', 261
DALY, L. H., 32, 165, 179 for general case, 259
DAVIDSON, G., 285 GEORGE, J. W., 199
DE ALT!, G., 180 GILLESPIE, R. J., 186, 187, 199
DE ANGELIS, B., 109 GLASSTONE, S., 271, 273
DECIUS, J. C., 132, 139, 173, 179, 180, GOULDEN, J. D. S., 179
259, 260, 262, 263 GREENWOOD, N. N., 197
Derivation of characters for selection GROSSMAN, W. E. L., 179
rules,279 Groups,249
XM(R) character, 279-281 classes, 249
Xa(R) character, 281-283 definition, 249
XE(R) character, 283, 284 finite, 249
Determination of proper correlation ta- infinite, 249
ble,78-83 representation, 249
Diagrams of normal vibrations, 275 subgroups, 249
C 2v ,275 Group theory
C 3v , 276 applications, 181
C4v ,277 GUTOWSKY, H. S., 198, 199
C oov ,275
D 3h , 276-278 HALFORD, R. S., 58, 70, 75, 77, 103, 108,
D 4h ,277 233
D oov ,275 Halford-Homig Method, 58, 70, 75, 77,
Oh,278 103, 108
Td ,272 HAMILTON, W. C., 192, 199
Index 289

HARADA, 1., 132 MARGENAU, H., 249, 258

HART, R. R., 130, 133 Matrix, 250
HAVIGHURST, R. J., 103, 108 definition, 250
HEATH, D. F., 131, 133, 165, 179 multiplication, 250
HEDBERG, K., 199 transpose, 250
HENRY, N. F. M., 108,224,233 types
Hermann-Mauguin system, 5, 28, 224 F matrix (F), 125, 126, 128, 129,
HERZBERG, G., 32, 56, 179, 191,271,273 132, 135, 136, 137, 141, 142,
HESTER, R. E., 179 144-146, 149, 150, 154, 156, 162
HIRAISHI, J., 179 fmatrix (1),124,143-147,154,159
HOCHSTRASSER, R. M., 32 o matrix (0), 127, 128, 136, 137,
HOFFMAN, C. J., 199 146-149, 155, 156, 164
HOLLAS, J. M., 32 g matrix (g), 127, 146, 147, 154, 155
HORNIG, D. F., 58, 70, 75, 77, 103, 108 U matrix (U), 117, 123, 135-137,
Hsu, C., 285 142-148, 153, 154, 160, 161
U' matrix (U'), 124, 137, 143-148,
IBERS, J. A., 192, 199 153, 163
Identity, 2 Mc DEVITT, N. T., 83, 109,247
Improper rotation, 36 MEISTER, A. G., 33, 56, 108, 137, 165,
IRISH, D. E., 108, 225, 233, 285 179,262,263
Irreducible representations, 22 MENARY, J. W., 108
characters, 22 MILLER, D. J., 179
MITRA, S. S., 58, 87, 89, 108
JAFFE, H. H., 32 Moleeules
JAMES, D. W., 108 A3 , 57, 58
JANZ, G. J., 179 At,59
JOLLY, W. L., 285 A,;,17
JONES, E. A., 198 AB, 57, 58
JONES, L. H., 32 AB2 , 9-10, 16, 57, 275
ABA,275
KEISER, W. E., 32
ABC, 57, 275
KENDALL, D. N., 32
AB. , 6-9, 57, 256
KHANNA, R. K., 109, 199
ABC., 57
KIM, H., 180
AB., 16,57,276
KOPELMAN, R., 109
AB5 , 18, 57, 278
LA BONVILLE, P., 109, 179 AB6 , 57, 278
LAu, K. K., 109 AB 7 , 57, 158
LA VILLA, R. E., 199 A,;Bs , 11, 17, 18
LEONG, W. H., 108 AIF3 ,107
LIEHR, A. D., 198 (AICl3)2 , 106
LINNETT, J. W., 131, 133, 165, 179 AuC14,57
LIPPINCOTT, E. K., 192, 199 BF3 , 7,16
LONSDALE, K., 108, 224, 233 BCI3 , 13
LORD, R. C., 185, 186, 199 BF.. (solid, melt), 172
LYNCH, M. A., 199 B2 C4,198
B2 Hs,32
MAccoLL, A., 178, 179 BeFl-, 172
MALM, J. G., 198, 199 BrCN,57
MANN, D. E., 198 BrF5 , 57, 197, 198
MATHEws, C. W., 285 CC4, 33, 35, 36, 57, 188, 190, 191
MATHIESON, A., 108 CD., 173
290 Index

Moleeules (Cant.) Moleeules (Cant.)

CF" 172 NH.(s), 13
CH., 166, 173 NH.NO., 92-100
CHCI.,166 NOCI,57
CHCI = CHCI (trans), 13 NO", 57
CH2 = C = CH2 , 13 N 2 0, 32, 57
CH.CI, 167 NI5N 140 16 , NI'NI5016, N15N15016,
CH.CHO,13 NI'NI'0'6, 107
CH.SnCI., 197 N20" 107, 194-196
COCl2 ,57 N",57
CO2 , 13, 20, 57 NpF6 ,17
c.H.,13 Ni(CNW,32
C6R., 13,57 N,S" 192-194
CIF., 31, 57, 198 N,S,H.,192
CI", 5 NSF.,107
Cr20.,30 OsF6 ,169
CsTeF5 ,197 P,,57
CuF2 ,12 PH,I, 99-102
CuO, 107 PCl,;, 18,57, 107
cyc1ohexane, 13 PF5 , 31, 198
cyc1opropane, 89-91 PdF6 ,169
DCH.,31 POF.,198
diacetylene, 107 POCI.,57
DOD,173 PtF6 ,170
D 2 CH2 ,31 PtF~- , 170
D20, 143, 173 PtCll-, 13, 16
GeF" 172 PuF6 , 171
H 2 ,5 PuBr.,76
HCI,6 pyrazine, 32
HOD,173 ReF6 ,169
H20, 10, 16,23, 57, 135, 138, 139, 143, RhF6 ,168
146-149, 151, 166, 173 RuF6 , 168
HgzCI2 , 103, 104 S8,57
HgS (a and ß), 108 SbCli- , 107
Hg (C == CC!)2, 107 SbSI,107
HgCI (C == CCI), 107 SF" 57, 188, 189, 197
H 2 0 2 ,13 SF6 ,13
H 2 S(s), 13 SiF" 172
IF5 , 13, 32, 185-187 S02,57
IF7 , 32, 57,182-185 SOC12 ,57
IrF6 ,170 TeFs ,197
KMnO, , 96-99 TiF, (gas), 172
KzCrO,,107 TiS,30
K.[Fe(CN)6l,84-86 TcF6 ,168
LaCI. , 105, 106 UF6 , 135, 156, 171
monochlorodiacetylene, 107 WF6 ,169
MoF6 , 168, 197 XeF" 188--192
NaNO., 58, 67, 68-71, 72-75 ZrS,107
naphthalene, 86-89 ZrSiO,,108
ND., 16,57 MUETTERTIES, E. L., 199
NH., 135, 150-152, 154, 156 MURPHY, G. M., 108,249,258,284
Index 291

MURRAY, M. J., 33, 56, 108 Potential force fields (Cant.)

valence force field, 131
NAGARAJAN, G., 108 Primitive lattice, 28-30
NAKAGAWA, 1., 84, 108, 179 Product rule, 167
NAKAMOTO, K., 32, 165, 178, 1~9 Proper rotation, 36
NEWBURY, L. G., 285
NEWNHAM, R. E., 109 RAo, K. N., 285
NEWTON, D. C., 106, 108, 109 REDLICH, 0., 180
NIELSEN, J. R., 265, 269 Reduction formula, 34, 37, 38, 51, 53
Normal coordinate treatment, 135 REIMANN, C. W., 109
molecules ROBERTS, H. L., 199
C2v , 138 ROBERTSON, J. M., 108, 199
C av , 150 ROSENTHAL, J. E., 108,284
Oh' 156 Ross, S.' D., 285
results, 165-167 Rotation axes, 3
several hexafluorides (Oh symmetry), Rotation-reflection axes, 4
168-171 Rotational components, 201
several tetrafluorides (Td symmetry), R x , R y , R z , 201
172 Rotation (R), 23
NUDELMAN, S., 87, 89, 108
SABATINI, A., 179
ORCHIN, M., 32, 285 SACCONI, L., 179
OVEREND, J., 132, 180 SALTHOUSE, J. A., 285
SARMA, A. C., 197
PALENIK, G. J., 96, 108 SCHACTSCHNElDER, J. H., 132, 178, 180
PARISEAU, J., 180 SCHATZ, P. N., 165, 179
PHILLIPS, W. D., 199 SCHERER, J. R., 132
PlOTROWSKI, E. A., 156, 180 SCHETTINO, V., 179
PISTORIUS, C. W. F. T., 179 SCHUMB, W. C., 199
Planes of symmetry, 4 Schoenflies system, 5, 28, 224
Ud, 4, 11, 16,22 Secular determinant and equation, 117,
Uh, 4-7, 12, 16, 17,21,22 148, 149
U v , 4-7, 9-10, 16,22,23 Selection rules, 33
Point group, 12 A a to AB type molecular, 57
definition, 12 derivation, 33
rules for ciassification, 14-16 linear mo1ecules, 50
selection rules, 33 nonlinear molecules, 33
types, 13 forbidden vibrations, 59-66
Polarizability components, 201 point group,
ll'xx, ll'xy, etc., 201 C oov , 50
Potential energy functions D ooh ,55
H2 0,142 Td ,33
NHa , 153 for systems involving translation, 58
MX., 119 SHAW, C. F., 285
Potential force fields, 111 SHERWOOD, P. M. A., 285
central force field, 130 SHIMANOUCHI, T., 132, 179
general quadratic potential function, SHURVELL, H. F., 179
119 SINCLAIR, V. C., 108
generalized valence force field, 131 Site group, 31
local symmetry force field, 116, 131 SLOWINSKI, E. J., 199
orbital valence force field, 131 SMITH, D. W., 199
292 Index

SNYDER, R. G., 132, 178, 180 Tables of site symmetries, 225

SONNESSA, A. J., 32 TANNER, K. N., 197
SOU DER, P. A., 180 TOBIN, M. C., 192, 199
Space group selection rules, 58 TOPPING, G., 178
examples, Translati.n (T), 23
cyclopropane, 89 Translation components, 201
Hg"CI2 ,103 Tx , Ty , Tz, 201
KMnO.,96 TURRELL, G., 285
K 3 [Fe(CN)6], 84
LaC13 ,104 Unambiguous choice of site symmetry,
NaN03 , 67, 70 75
naphthalene, 87 Update bibliography, 285
Nli.N03 ,91 UREY, H. C., 132
PH.I,99
Species of vibrations, 21 VENKATARAYUDU, T., 58, 108
symbols (linear molecules), 21 VENKATESWARLU, K., 165, 179
symbols (nonlinear molecules), 21 Vibration (Q), 23
STAMMREICH, H., 179
STEELE, D., 285 WAIT, S. C., 179
STEPHENSON, C. V., 198 WALKER, A., 33
STEPHENSON, G., 258 WALKER, M., 108
STRAUGHAN, B. P., 197 WALL, M. C., 179
Sum rule, 173 WALTER, J. L., 108
Summary of Fand G matrices, 174 WARD, A. T., 179
Oh molecules, 174 WARD, C. H., 197
D' h molecule, 174 WARE, M. J., 285
Td molecule, 175 WAUGH, J. S., 199
D 3h (AB 3 ) moleeule, 176 WEINSTOCK, B., 198
C3.(AB3 ) molecule, 176 WELLS, A. F., 27
C 2V molecule, 177 WEYL, H., 32
SUNDARAM, S., 165, 179, 180 WHEATLEY, P. J., 24-28
SUSZEK, F., 180 WHITE, J. E., 32
Symmetry,1 WHITE, W. B., 109
center, 4 WIBERLEY, S. E., 32,165,179,260
classes of operations, 22 WILSON, E. B., 132, 135, 137, 148, 173,
coordinate, 117, 135-137, 151, 157 179,180,259,260,263
definition, 1 WINSTON, H., 108
effects on normal coordinates of H2 0, WOODWARD, L. A., 179, 199
23 Wu, E., 180
elements in condensed state, 24 WYCKOFF, R. W. C., 75-77, 91, 93, 96,
operations, 5, 22 99, 101, 108
planes, 4
science, 1 YERANOS, W. A., 133, 178, 180
space, 24
structural chemistry, 2 ZACHARIASEN, W. H., 32
Symmetry elements, 2 ZELDIN, H., 14, 32
SZYMANSKI, H. A., 32, 258 ZIOMEK, J. S., 32, 156, 180,258