Atkins & Friedman: Molecular Quantum Mechanics 5e

C05 p. 1
Chapter 5
Group theory
All the following material P.W. Atkins and R.S. Friedman.
Exercises

5.1 (a) E,
h
, 2C
3
, 2S
3
, 3C
2
, 3
v
;

(b) E, C
2
,
v
, '
v
;

(c) E, 2C
6
, 2C
3
, C
2
, 3C
2
', 3C
2
", i,

2S
3
, 2S
6
, 3C
2
,
h
, 3
d
, 3
v
.

5.2 (a) E, C
2
(z), C
2
(y), C
2
(x), i, (xy), (xz), (yz);

(b) E, C
2
, i,
h
;

(c) E, C
2
, i,
h
.

5.3 (a) D
3h,
(b) C
2v
, (c) D
6h
.

5.4 (a) D
2h,
(b) C
2h,
(c) C
2h.


5.5(a) H
2
O: E, C
2
, 2o
v
; hence
2v
. C
(b) CO
2
: E, C

, C
2
C

, o
h
; hence
h
D

(c) C
2
H
4
: E, C
2
,
2
2C' C
2
, o
h
; hence
2h
D
(d) cis-ClHC=CHCl: E, C
2
, 2o
v
; hence
2v
C
5.6 (a) trans-ClHC=CHCl: E, C
2
, o
h
; hence
2h
C
(b) Benzene: E, C
6
,
2
6 , C' o
h
; hence
6h
D
(c) Naphthalene: E, C
2
,
2
2 , C' o
h
; hence
2h
D
Atkins & Friedman: Molecular Quantum Mechanics 5e


C05 p. 2
(d) CHClFBr: E; hence
1
C
(e) B(OH)
3
: E, C
3
, o
h
; hence
3h
C
Exercise: Classify chlorobenzene, anthracene, H
2
O
2
, S
8

5.7 (a) PF
5
(pentagonal pyramid), corannulene C
20
H
10
,

(b) all cis-C
5
H
5
F
5
(planar), (c) Fe(C
5
H
5
)
2
(staggered).

5.8 T
d
: CH
4
; O
h
: SF
6
; I: C
60
.

5.9 (a) The group multiplication table for C
s
is as follows:
First: E
Second:
E E
E

(b) The group multiplication table for D
2
is as follows:

First: E C
2
(z) C
2
(y) C
2
(x)
Second:
E E C
2
(z) C
2
(y) C
2
(x)
C
2
(z) C
2
(z) E C
2
(x) C
2
(y)
C
2
(y) C
2
(y) C
2
(x) E C
2
(z)
C
2
(x) C
2
(x) C
2
(y) C
2
(z) E

5.10 We need to confirm that (RS)T = R(ST) for all elements R, S and T that appear in the
group multiplication table for C
2v
in Example 5.2.

Atkins & Friedman: Molecular Quantum Mechanics 5e


C05 p. 3
(EC
2
)o
v
= C
2
o
v
=
v
o' = E(C
2
o
v
)
(EC
2
)
v
o' = C
2
v
o' = o
v
= E(C
2
v
) o'
(Eo
v
)C
2
= o
v
C
2
=
v
o' = E(o
v
C
2
)
(Eo
v
)
v
o' = o
v
v
o' = C
2
= E(o
v
v
) o'
(E
V 2
)C o' =
V
o' C
2
= o
V
= E(
V
o' C
2
)
(E
v v
) o o ' =
v
o' o
v
= C
2
= E(
v
o' o
v
)
(C
2
o
v
)E =
v
E o' =
v
o' = C
2
(o
v
E)
(C
2
o
v
)
v
o' =
v v
o o ' ' = E = C
2
(o
v
v
) o'
(C
2
v
)E o' = o
v
E = o
v
= C
2
(
v
)E o'

2 v v
( ) C o o ' = o
v
o
v
= E = C
2
(
v v
) o o '

v v
( )E o o' = C
2
E = C
2
= o
v
(
v
) E o'

v v 2
( )C o o' = C
2
C
2
= E = o
v
v 2
( ) C o'
Since the elements commute in the group C
2v
, if (RS)T = R(ST), then (SR)T = S(RT). For
example:
v v 2
( )C o o ' = (o
v
v
) o' C
2
= o
v
(
v
o' C
2
) = o
v
(C
2
v
) o' = (o
v
C
2
)
v
o' =
v
o' (o
v
C
2
)
Exercise: Confirm that the elements in the C
3v
group multiplication table of Table 5.2
multiply associatively.



Atkins & Friedman: Molecular Quantum Mechanics 5e


C05 p. 4
5.11 Write f = (H1s
A
, H1s
B
, O2s, O2p
x
, O2p
y
, O2p
z
); then Ef = f = f1; hence D(E) = 1, the 6
6 unit matrix.
C
2
f = (H1s
B
, H1s
A
, O2s, O2p
x
, O2p
y
, O2p
z
)
= f
0 1 0 0 0 0
1 0 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(
(
(
(

(
(

(

= fD(C
2
)
o
v
f = (H1s
B
, H1s
A
, O2s, O2p
x
, O2p
y
, O2p
z
)
= f
0 1 0 0 0 0
1 0 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(
(
(
(
(
(

(

= fD(o
v
)

v
o' f = (H1s
A
, H1s
B
, O2s, O2p
x
, O2p
y
, O2p
z
)
= f
1 0 0 0 0 0
0 1 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(
(
(
(

(
(
(

= fD
v
( ) o'
Exercise: Replace the p-orbitals by d-orbitals, and find the matrix representation.
5.12
Atkins & Friedman: Molecular Quantum Mechanics 5e


C05 p. 5
D(C
2
)D(C
2
) =
0 1 0 0 0 0 0 1 0 0 0 0
1 0 0 0 0 0 1 0 0 0 0 0
0 0 1 0 0 0 0 0 1 0 0 0
0 0 0 1 0 0 0 0 0 1 0 0
0 0 0 0 1 0 0 0 0 0 1 0
0 0 0 0 0 1 0 0 0 0 0 1
( (
( (
( (
( (
( (

( (
( (

( (


=
1 0 0 0 0 0
0 1 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(
(
(
(
(
(
(

= D(E); reproducing
2
2
C = E
D(o
v
)D(C
2
) =
0 1 0 0 0 0 0 1 0 0 0 0
1 0 0 0 0 0 1 0 0 0 0 0
0 0 1 0 0 0 0 0 1 0 0 0
0 0 0 1 0 0 0 0 0 1 0 0
0 0 0 0 1 0 0 0 0 0 1 0
0 0 0 0 0 1 0 0 0 0 0 1
( (
( (
( (
( (
( (

( (
( (

( (


=
1 0 0 0 0 0
0 1 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(
(
(
(

(
(
(

= D
v
( ); o' reproducing o
v
C
2
=
v
o'
Exercise: Confirm these multiplications for the representatives constructed using d-
orbitals.
5.13 Denote s
1
+ s
2
as s'

and s
1
s
2
as s". Since

Atkins & Friedman: Molecular Quantum Mechanics 5e


C05 p. 6
(s', s", 02s, 02p
x
, 02p

,02p
z
) = (s
1
, s
2
,02s, 02p
x
, 02p

,02p
z
)
1 1 0 0 0 0
1 1 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(

(
(
(
(
(
(


the matrix c is given by
c =
1 1 0 0 0 0
1 1 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(

(
(
(
(
(
(





with an inverse given by

c
-1
=
1/ 2 1/ 2 0 0 0 0
1/ 2 1/ 2 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(

(
(
(
(
(
(



5.14 The representatives for C
2
and
v
in the basis (H1s
A
, H1s
B,
O2s, O2p
x,
O2p
y,
O2p
z
) are

given in Exercise 5.11 and denoted D(C
2
) and D(
v
), respectively. The

representatives in the new basis are given by c
1
D(C
2
)c and c
1
D(
v
)c:



Atkins & Friedman: Molecular Quantum Mechanics 5e


C05 p. 7
D
i
(C
2
) =
1/ 2 1/ 2 0 0 0 0
1/ 2 1/ 2 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(

(
(
(
(
(
(

0 1 0 0 0 0
1 0 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(
(
(
(

(
(

(

1 1 0 0 0 0
1 1 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(

(
(
(
(
(
(

=
1/ 2 1/ 2 0 0 0 0
1/ 2 1/ 2 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(

(
(
(

(
(

(

1 1 0 0 0 0
1 1 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(

(
(
(
(
(
(

=
1 0 0 0 0 0
0 1 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(

(
(
(

(
(

(








Atkins & Friedman: Molecular Quantum Mechanics 5e


C05 p. 8
D
i
(o
v
) =
1/ 2 1/ 2 0 0 0 0
1/ 2 1/ 2 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(

(
(
(
(
(
(

0 1 0 0 0 0
1 0 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(
(
(
(
(
(

(

1 1 0 0 0 0
1 1 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(

(
(
(
(
(
(

=
1/ 2 1/ 2 0 0 0 0
1/ 2 1/ 2 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(

(
(
(
(
(

(

1 1 0 0 0 0
1 1 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(

(
(
(
(
(
(

=
1 0 0 0 0 0
0 1 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(

(
(
(
(
(

(





5.15 H has the full symmetry of the system [definition of symmetry operation], and so it is a
basis for A
1
or the equivalent totally symmetric irreducible representation. Therefore,
'H spans I' I if ' spans I' and spans I. But I' I contains A
1
only if I' = I.
Therefore, the integral vanishes when ' and belong to different symmetry species.
Exercise: Under what circumstances may a molecule possess a permanent electric
dipole moment?

5.16 The point group of a regular tetrahedron is T
d
: three-dimensional irreducible
representations are allowed; therefore the maximum degeneracy is 3. (Accidental
degeneracies could increase this number.)
Atkins & Friedman: Molecular Quantum Mechanics 5e


C05 p. 9
Exercise: What is the maximum degeneracy of molecular obitals of (a) benzene, (b)
anthracene, (c) an icosahedral molecule?
5.17 _(C
120
) =
3
2
sin( 120)/sin 60 = 0; _(E) = 3
_(o
v
) = 1 [because p
y
p
y
, p
x
p
x
, p
z
p
z
]
The characters for (E, 2C
3
, 3o
v
) are therefore (3,0,1). Therefore, the orbitals span
1
A E. +
Exercise: What symmetry species would be spanned if the p-orbitals were replaced by
(a) f-orbitals, (b) g-orbitals?
5.18 Carbon dioxide is of point group D
h
. The initial wavefunction is assumed to be of
symmetry
u

(or A
2u
); from the character table in Resource section 1, z spans
u
+
(or
A
1u
). By inspection of the character table,
A
2u
A
1u
= A
2g

Therefore, the symmetry of the excited state must be
g 2g
(or A ).

E
Exercise: Repeat for y-polarized radiation.
5.19 We need to show that there is a symmetry transformation of the group that transforms

C
3
+
into C
3

.There are three C

2
rotation axes in the point group D
3
, each of which is its

own inverse. For any of these C
2
axes, the joint operation C
2
1
C
3
+
C
2
yields C
3

.
Problems
5.1 The sums of the diagonal elements in the matrices in Exercise 5.11 are
_(E) = 6, _(C
2
) = 0, _(o
v
) = 2, _
v
( ) o' = 4
Use eqn 5.22 in the form
Atkins & Friedman: Molecular Quantum Mechanics 5e


C05 p. 10
a
l
= (1/4){6_
(l)
(E) + 0 + 2_
(l)
(o
v
) + 4_
(l)
v
( )} o'
Then
a(A
1
) =
1
4
{6 + 0 + 2 + 4} = 3 a(A
2
) =
1
4
{6 + 0 2 4} = 0
a(B
1
) =
1
4
{6 0 + 2 4} = 1 a(B
2
) =
1
4
{6 0 2 + 4} = 2
Hence, the reduction is into
1 1 2
3A B 2B + +
Draw up the following Table:
H1s
A
H1s
B
O2s O2p
x
O2p
y
O2p
z

E H1s
A
H1s
B
O2s O2p
x
O2p
y
O2p
z

C
2
H1s
B
H1s
A
O2s O2p
x
O2p
y
O2p
z

o
v
H1s
B
H1s
A
O2s O2p
x
O2p
y
O2p
z

v
o' H1s
A
H1s
B
O2s O2p
x
O2p
y
O2p
z

Form f
(A
1
)
by using p
(A
1
)
=
1
(A )
1
4
( ) .
R
R R _

From column 1,
f
(A
1
)
=
1
4
{H1s
A
+ H1s
B
+ H1s
B
+ H1s
A
} =
1
2
{H1s
A
+ H1s
B
}
From column 2, find the same. From column 3, f
(A
1
)
= O2s, from columns 4 and 5
obtain 0. From column 6, f
(A
1
)
= O2p
z
. Hence
1
(A )
1
A B
2
{ (H1 H1 ), O2s, O2p }
z
s s = + f
Form f
(B
1
)
: only column 4 gives a non-zero quantity.
1
(B )
O2p
x
= f
Atkins & Friedman: Molecular Quantum Mechanics 5e


C05 p. 11
Form f
(B
2
)
: columns 3,4,6 give zero; columns 1,2, and 5 give
2
(B )
1
B A
2
{ (H1s H1s ), O2p }
y
= f
Only
1 2
(A ) (B )
1 1
and f f involve linear combinations; the matrix of coefficients (Section
5.6) is therefore given by
{
2
1
(H1s
A
+ H1s
B
),
2
1
(H1s
B
H1s
A
), O2s, O2p
x
, O2p
y
, O2p
z
}
= {H1s
A
, H1s
B
, O2s, O2p
x
, O2p
y
, O2p
z
}
1 1
2 2
1 1
2 2
0 0 0 0
0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(
(
(
(
(
(
(
(


Consequently,
c =
1 1
2 2
1 1
2 2
0 0 0 0
0 0 0 0
0 0 1 0 0 0
,
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(
(
(
(
(
(
(
(

c
1
=
1 1 0 0 0 0
1 1 0 0 0 0
0 0 1 0 0 0
0 0 0 1 0 0
0 0 0 0 1 0
0 0 0 0 0 1
(
(

(
(
(
(
(
(


Then, from eqn 5.7b, showing only the H1s-combinations:
D'(E) =
1 1
2 2
1 1
2 2
1 1 1 0 1 0
1 1 0 1 0 1
| | | | | | | |
=
| | | |
\ . \ . \ .
\ .

D'(C
2
) =
1 1
2 2
1 1
2 2
1 1 0 1 1 0
1 1 1 0 0 1
| | | | | | | |
=
| | | |
\ . \ . \ .
\ .

Atkins & Friedman: Molecular Quantum Mechanics 5e


C05 p. 12
D'(o
v
) =
1 1
2 2
1 1
2 2
1 1 0 1 1 0
1 1 1 0 0 1
| | | | | | | |
=
| | | |
\ . \ . \ .
\ .

D'
v
( ) o' =
1 1
2 2
1 1
2 2
1 1 1 0 1 0
1 1 0 1 0 1
| | | | | | | |
=
| | | |
\ . \ . \ .
\ .

Because these matrices are diagonal (and therefore also block-diagonal), and the
remainder of D(R) are already diagonal, the entire representation is (block-) diagonal.
Exercise: Consider a representation using the basis (p
x
, p
y
, p
z
) on each atom in a C
2v

AB
2
molecule. Find the representatives, the symmetry-adapted combinations, and the
block-diagonal representations.

5.4
D(
3
C
+
(A))D(
3
C

(A))
=
1 0 0 0 1 0 0 0 1 0 0 0
0 0 0 1 0 0 1 0 0 1 0 0
0 1 0 0 0 0 0 1 0 0 1 0
0 0 1 0 0 1 0 0 0 0 0 1
( ( (
( ( (
( ( (
=
( ( (
( ( (

= D(E)
D
4
(S
+
(AC))D
3
(C

(B))
=
0 0 0 1 0 0 0 1 0 0 1 0
1 0 0 0 0 1 0 0 0 0 0 1
0 1 0 0 1 0 0 0 0 1 0 0
0 0 1 0 0 0 1 0 1 0 0 0
( ( (
( ( (
( ( (
=
( ( (
( ( (

= D
4
(S

(CD))
D
4
(S
+
(AC))D(
3
C

(C))
=
0 0 0 1 0 1 0 0 1 0 0 0
1 0 0 0 0 0 0 1 0 1 0 0
0 1 0 0 0 0 1 0 0 0 0 1
0 0 1 0 1 0 0 0 0 0 1 0
( ( (
( ( (
( ( (
=
( ( (
( ( (

= D(o
d
(AB))
Atkins & Friedman: Molecular Quantum Mechanics 5e


C05 p. 13
Exercise: Check three of the group multiplications for the representation developed in
the Exercise accompanying problem 5.2.


5.7 (a) _(A
2
) _(B
1
) _(B
2
)
= (1, 1, 1, 1) (1, 1, 1, 1) (1, 1, 1, 1) = (1, 1, 1, 1) = _(A
1
)
therefore,
2 1 2 1
A B B A = in C
2v

(b) _(A
1
) _(A
2
) _(E)
= (1, 1, 1) (1, 1, 1) (2, 1, 0) = (2, 1, 0) = _(E);
therefore,
1 2
A A E E = in C
3v

(c) _(B
2
) _(E
1
) = (1, 1, 1, 1, 1, 1) (2, 2, 1, 1, 0, 0)
= (2, 2, 1, 1, 0, 0) = _(E
2
)
therefore,
2 1 2
B E E = in C
6v

(d) _(E
1
) _(E
1
) = (2, 2 cos |, 0) (2, 2 cos |, 0)
= (4, 4 cos
2
|, 0) =(4, 2 + 2 cos 2|, 0)
= _(A
1
) + _(A
2
) + _(E
2
)
therefore,
1 1 1 2 2
E E A A E = + + in C
v

(Alternatively: H H = E
+
+ E

+ A)
(e) _(T
1
) _(T
2
) _(E)
= (3, 0, 1, 1, 1) (3, 0, 1, 1, 1) (2, 1, 2, 0, 0) = (18, 0, 2, 0, 0)
Decompose this using a
l
= (1/24){18_
(l)
(E) + 6_
(l)
(C
2
)} [eqn 5.23].
a(A
1
) = (1/24){18 + 6} = 1 a(A
2
) = (1/24){18 + 6} = 1
Atkins & Friedman: Molecular Quantum Mechanics 5e


C05 p. 14
a(E) = (1/24){36 + 12} = 2
a(T
1
) = (1/24){54 6} = 2 a(T
2
) = (1/24){54 6} = 2
Therefore,
1 2 1 2 1 2
T T E A A 2E 2T 2T in O = + + + +
Exercise: Analyse the following direct products: E E A
2
in C
3v
, A
2u
E
1u
in D
6h
,
and
2 2
1g 2g u
T T E in O
h
.
5.10 (a)

2
1 1 2
a b b : A
1
A
1
B
1
B
2
= B
1
B
2
= A
2
;
1 3
2 2
A and A may arise.
(b) (i) a
2
e : A
2
E = E;
1 3
E and E may arise.
(ii) e
2
: E E = A
1
+ [A
2
] + E;
1 3 1
1 2
A , A , E may arise.
(c) (i) a
2
e : A
2
E = E;
1 3
E and E may arise.
(ii) et
1
: E T
1
= T
1
+ T
2
;
1 3 1 3
1 1 2 2
T , T , T , and T may arise.
(iii) t
1
t
2
: T
1
T
2
= A
2
+ E + T
1
+ T
2
;
1 3 1 3 1 3 1 3
2 2 1 1 2 2
A , A , E, E, T , T , T , and T may
arise.
(iv)
2
1
t : T
1
T
1
= A
1
+ E + [T
1
] + T
2
;
1 1 3 1
1 1 2
A , E, T , and T may arise.
(v)
2
2
t : T
2
T
2
= A
1
+ E + [T
1
] + T
2
;
1 1 3 1
1 1 2
A , E, T , and T may arise.
(d) (i) e
2
: E E = A
1
+ [A
2
] + E;
1 3 1
1 2
A , A , and E may arise.
(ii) et
1
: E T
1
= T
1
+ T
2
;
1 3 1 3
1 1 2 2
T , T , T , and T may arise.
(iii)
2
2
t : T
2
T
2
= A
1
+ E + [T
1
] + T
2
;
1 1 3 1
1 1 2
A , E, T , and T may arise.
Atkins & Friedman: Molecular Quantum Mechanics 5e


C05 p. 15
Exercise: Classify the term that may arise from d
2
in R
3
, o
1
t
1
in C
v
, t
2
in D
h
,
1 1
g 1u
e t
in O
h
, and
2
1g
e in D
6h
.

5.13 (a) In C
2v
translations span A
1
+ B
1
+ B
2
; hence a
2
A
1
term may make a transition to A
1


2
A
1
=
2
A
1
, B
1

2
A
1
=
2
B
1
, and B
2

2
A
1
=
2
B
2
and a
2
B
1
term may make trantitions to
A
1

2
B
1
=
2
B
1
, B
1

2
B
1
=
2
A
1
, and B
2

2
B
1
=
2
A
2
. In D
h
, translations span
u
+
E + H
u
.
Therefore, because
u g u
+
E E = E and H
u

g

E = H
u
, transitions to
3
u

E and
3
H
u
are
allowed.
(b) In C
2v
rotations span A
2
+ B
1
+ B
2
. Then, because A
1
(A
2
+ B
1
+ B
2
) = A
2
+ B
1
+
B
2
, transitions to
2
A
2
,
2
B
1
, and
2
B
2
are allowed for NO
2
. Because B
1
(A
2
+ B
1
+
B
2
) = B
2
+ A
1
+ A
2
, transitions to
2
B
2
,
2
A
1
, and
2
A
2
are allowed for ClO
2
. In D
h
,
rotations transform as
g

E + H
g
, and because
g

E (
g

E + H
g
) =
g
+
E + H
g
,
transtions to
3
g
+
E and
3
H
g
are allowed in O
2
.
Exercise: What electric and magnetic dipole transitions may take place from the E
1g
,
E
2u
, and B
2g
terms of benzene?


5.16 For an f orbital, l = 3. We calculate the characters from eqn 5.47b with l = 3. (a)

For a C
3v
environment, we only consider the symmetry operations E and C
3
for which

angles can be identified. This is equivalent to working in the rotational subgroup C
3
.

For E, = 0 and = 7; for C
3
, = 2/3 and = 1. We now use eqn 5.23 with h = 6

and find a(E) = 2. We can use h = 6 because the character for
v
is zero for the
Atkins & Friedman: Molecular Quantum Mechanics 5e


C05 p. 16

irreducible representation E. However, since the characters for
v
are nonzero for the

irreducible representations A
1
and A
2
,

we must revert to using the rotational subgroup

C
3
. In this case the angles are = 0 for E, = 2/3 for C
3
and = 4/3 for C
3
2
; this

yields characters (7, 1, 1) for (E, C
3
, C
3
2
) and use of eqn 5.23 with h = 3 (the order of

the group C
3
) yields a(A) = 3. Therefore, the symmetry species are 3A + 2E. (b) For a

T
d
environment, we only consider the symmetry operations E, C
2
and C
3
for which

angles can be identified. Therefore we work in the rotational subgroup T. For E, =

0 and = 7; for C
3
, = 2/3 and = 1; for C
3
2
, = 4/3 and = 1; and for C
2
, =

and = 1. We now use eqn 5.23 with h = 12 (for group T) and find a(A) = 1 and

a(T) = 2. Therefore, the symmetry species are A + 2T.


5.19 We have shown in Section 5.18 that the difference between two infinitesimal rotations

is equivalent to a single infinitesimal rotation and that the reverse argument implies

the angular momentum commutation rules. We show here that the commutation

relation [l
x
, l
y
] = il
z
and the definition of angular momentum in terms of position and

linear momentum operators implies the fundamental quantum mechanical

commutation rule [q, p
q
] = i and, as a result, the latter commutation rule can be

considered a manifestation of three-dimensional space. We begin by expanding [l
x
, l
y
]:

[l
x
, l
y
] = [yp
z
zp
y
, zp
x
xp
z
]

= [yp
z
, zp
x
] [yp
z
, xp
z
] [zp
y
, zp
x
] + [zp
y
, xp
z
]

= yp
z
zp
x
zp
x
yp
z
(yp
z
xp
z
xp
z
yp
z
) (zp
y
zp
x
zp
x
zp
y
) + (zp
y
xp
z
xp
z
zp
y
)

= yp
x
[p
z
, z] 0 0 + xp
y
[z, p
z
]
Atkins & Friedman: Molecular Quantum Mechanics 5e


C05 p. 17

= [z, p
z
]{xp
y
yp
x
}

Since l
z
= xp
y
yp
x
, the relation [l
x
, l
y
] = il
z
immediately implies that [z, p
z
] = i, the

fundamental quantum mechanical selection rule.