Chemical Applications of Group Theory

We have learnt the point group theory of molecular

symmetry. We shall learn how to use this theory in
our chemical research.
1. Representation of groups
1.1 Matrix representation and reducible representation
1.2 Reducing of representations
Suppose that we have a set of n-dimensional matrices, A, B,
C, , which form a representation of a group. These n-D
matrices themselves constitute a matrix group.
If we make the same similarity transformation on each matrix,
we obtain a new set of matrices,
This new set of matrices is also a representation of the group.
If A is a blocked-factored matrix, then it is easy to prove that
B,C also are blocked-factored matrices.
A
1
,A
2
,A
3
are n
1
,n
2
,n
3
-D submatrices with n= n
1
+ n
2
+ n
3
+ .
Furthermore, it is also provable that the various sets of
submatrices
{A
1
,B
1
,C
1
}, {A
2
,B
2
,C
2
}, {A
3
,B
3
,C
3
}, {A
4
,B
4
,C
4
},
are in themselves representations of the group.
We then call the set of matrices A,B,C, a reducible
representation of the group.
If it is not possible to find a similarity transformation to reduce
a representation in the above manner, the representation is
said to be irreducible.
The irreducible representations of a group is of fundamental
importance.
2. Character Tables of Point Groups
Bases
2.1 Construction of Character Table
These translation vectors constitute a set of bases of C
2v
group.
2.2 symmetry species: Mulliken symbols
All 1-D irreducible reps. are labeled by either A or B, 2-D
irreducible rep. by E, 3-D irreducible rep. by T and so on.
A: symmetric with respect to C
n
rotation, i.e., _(C
n
)=1.
B: asymmetric with respect to C
n
rotation, i.e., _(C
n
)=-1.
Subscriptions 1 or 2 designates those symmetric or asymmetric
with respect to a C
2
or a o
v
.
Subscripts g or u for universal parity or disparity.
Superscripts or designates those symmetric or asymmetric with
respect to o
h
2.3 Symmetry of molecular properties
This formula was derived from the Great orthorgonality theorem.
3. Symmetry adapted Linear Combinations of AOs
A convenient way to construct MOs
Symmetry of wavefunctions of a molecule
Symmetry Operation on Schrdinger Eq.
= E R = RE
R
RR
-1
R = ER
R = ER
R is also an eigenvector of
, with the same eigenvalue
E as corresponds to.
Symmetry of wavefunctions
If eigenvalue E is not degenerate, then
R = c
Which means is a basis for some 1-D I.R..
Symmetry of wavefunctions
If eigenstate E is l-fold degenerate, then
Which means set {
1
,
2
, ,
l
} is a basis for this l-D I.R.
E
{
1
,
2
, ,
l
}
Symmetry of wavefunctions
In LCAO approach of MO theory, we have
So we need to solve the secular equation
Symmetry of wavefunctions
We can transform the original bases of AOs into Linear
Combinations of AOs which have the same properties of
some I.R.s (Symmetry Adapted Linear Combination),
therefore the Secular Equation is block diagonalized.

AO SALC
?
Symmetry of wavefunctions

H-ES
I
1
I
2
...
...
0
0
Block Diagonalized
AO
SALC
n n
n
2
n
2
n
1
n
1
I
Symmetry of wavefunctions

Step 1 Reduce the REP spanned by the AO basis.
Obtain the n
i
s for each I.R.
Step 2 Construct n
i
SALCs for each I.R..
Step 3 Transform the hamiltonian matrix into block
diagonalized form, and solve it.
Example 1:
Neglecting the O 1s orbital/electrons.
H
2
O
LCAO with the following atomic orbitals
O: 2s; 2p
x
, 2p
y
, 2p
z
2H: 1s
a
, 1s
b
Symmetry: C
2v
H
2
O
C
2v
I C
2
o
v
o
v
'
A
1
A
2
B
1
B
2
z
xy
x,xz
y,yz
1 1 1 1
1 1 -1 -1
1 -1 1 -1
1 -1 -1 1
Character Table
Symmetry of AOs
from Oxygen
A
1
: 2s, 2p
z
B
1
: 2p
x
B
2
: 2p
y
Symmetry Reduction of 2-D Bases Set {1s
a
, 1s
b
}
C
2v
I C
2
o
v
o
v
'
A
1
A
2
B
1
B
2
z
xy
x,xz
y,yz
_(R) 2 0 0 2
1 1 1 1
1 1 -1 -1
1 -1 1 -1
1 -1 -1 1
Two 1-D REPs
SALC - Symmetry Adapted Linear Combination of AOs
For this trivial problem, it is very simple, we
intuitively determined the new basis as
A
1
:
+ +
+
-
B
2
:
H2O
A
1
symmetry AOs or SALCs for LCAO
A
1
:
O2s, O2p
z
Too complicated for analysis!
H2O- Hybridization of Oxygens 2s and 2p
z
+
-
2s
2p
z
h
h
Hybridization
H2O- Hybridization of Oxygens 2s and 2p
z
h h
Small, not effective bonding
Large, effective bonding
H2O- Chemical Bonding in A
1
REP
h
h
+
+ +
+
+ -
Non-bonding
H2O- Chemical Bonding in B
2
REP
2p
y
-
+
+
- +
-
-
+
-
+
+ -
H2O- Summary on Chemical Bonding
O
2H H
2
O
1s
2s
2p
h, h
b
1
, b
2
1s(a,b)
1a
1
2a
1
3a
1
4a
1
1b
2
2b
2
1b
1
H2O- Summary on Molecular Energy Level Sequences
+
+ +
2a
1
3a
1
+
+
-
4a
1
-
+
-
+
1b
2
+
-
+ -
2b
2
1b
1 s s
s
s s
Use Projection operator to construct SALCs
Definition:
for j-th ir. rep. of the point group. This equation was
derived from the great orthogonality theorem.
A non-normalized SALC can be constructed from
bases set by the formula:
Example: t-MOs of C
3
H
3
(D
3h
)
I = A
2
"
+ E
"
However, it is more convenient to
reduce its symmetry to D
3
. Then we
have
I = A
2
+ E
I

Using orthogonality and normalization, we have

I
t
3 0 -1 I
t
= A
2
+ E
Another way to derive the third MO:
1. Find an operation to covert the second wavefunction into an
nonequivalent one (not +/- of the original one). A C
3
operation
works well. Then we have
2. A linear combination of this new one and the original one gives
rise to
A general simplification
Reducing the symmetry to C
3
subgroup.
I
t
3 0 0 I
t
= A+ E
Example 2: C
6
H
6
D
6h
C
6
I
t
6 0 0 0 0 0 I
t
= A+ B + E
1
+ E
2
C
6
H
6
D
6h
C
6
I 6 0 0 0 0 0 I = A+ B + E
1
+ E
2
Similarly, we have
CO
2
has 3 modes of vibration
Vibrational spectroscopy
O=C=O O=C=O O=C=O
Infra-red inactive -
no dipole change
IR active
IR active
H
2
O has 3 modes of vibration
IR
active
IR active IR active
H
O
H
H
O
H
H
O
H
Number of active modes tells us about symmetry
Molecular vibrations - number of modes
4 atoms - can move independently in x, y, z directions
x
y
z
x
y
z
x
y
z
x
y
z
3N degrees of freedom for a N-atom molecule.
If atoms fixed, there are: 3 translational degrees
3 rotational degrees
and the rest (3N-6) are vibrational modes
No. of modes of each symmetry species
Example - SiH
2
Cl
2
Point group C
2v
Character table
C
2v
E C
2
o
v
(xz) o
v
(yz) h = 4
A
1
+1 +1 +1 +1 z x
2
, y
2
, z
2
A
2
+1 +1 -1 -1 R
z
xy
B
1
+1 -1 +1 -1 x, R
y
xz
B
2
+1 -1 -1 +1 y, R
x
yz
Si
Cl
2
H
1
Cl
1
H
2
z
x
y
Draw x, y and z vectors on all atoms
Count +1, -1, 0 if vector transforms to itself, minus
itself, or moves
Perform symmetry operations
Character table
C
2v
E C
2
o
v
(xz) o
v
(yz) h = 4
A
1
+1 +1 +1 +1 z x
2
, y
2
, z
2
A
2
+1 +1 -1 -1 R
z
xy
B
1
+1 -1 +1 -1 x, R
y
xz
B
2
+1 -1 -1 +1 y, R
x
yz
Si
Cl
2
H
1
Cl
1
H
2
z
x
y
Operation E
Si atom x transforms into Si x count +1
y transforms into Si y count +1
z transforms into Si z count +1
total +3
Same for other 4 atoms grand total +15
Character table
C
2v
E C
2
o
v
(xz) o
v
(yz) h = 4
A
1
+1 +1 +1 +1 z x
2
, y
2
, z
2
A
2
+1 +1 -1 -1 R
z
xy
B
1
+1 -1 +1 -1 x, R
y
xz
B
2
+1 -1 -1 +1 y, R
x
yz
Si
Cl
2
H
1
Cl
1
H
2
z
x
y
Operation C
2
Si atom x transforms into Si -x count -1
y transforms into Si -y count -1
z transforms into Si z count +1
total -1
H
1
and H
2
move - swap places count 0
Cl
1
and Cl
2
swap places count 0
grand total -1
Character table
C
2v
E C
2
o
v
(xz) o
v
(yz) h = 4
A
1
+1 +1 +1 +1 z x
2
, y
2
, z
2
A
2
+1 +1 -1 -1 R
z
xy
B
1
+1 -1 +1 -1 x, R
y
xz
B
2
+1 -1 -1 +1 y, R
x
yz
Si
Cl
2
H
1
Cl
1
H
2
z
x
y
Operation o
v
(xz) Si atomx transforms into Si x count +1
y transforms into Si -y count -1
z transforms into Si z count +1
total +1
H
1
and H
2
also lie in xz plane, and behave as Si count +1 each
Cl
1
and Cl
2
swap places count 0
grand total +3
Character table
C
2v
E C
2
o
v
(xz) o
v
(yz) h = 4
A
1
+1 +1 +1 +1 z x
2
, y
2
, z
2
A
2
+1 +1 -1 -1 R
z
xy
B
1
+1 -1 +1 -1 x, R
y
xz
B
2
+1 -1 -1 +1 y, R
x
yz
Si
Cl
2
H
1
Cl
1
H
2
z
x
y
Operation o
v
(yz) Si atomx transforms into Si -x count -1
y transforms into Si y count +1
z transforms into Si z count +1
total +1
H
1
and H
2
swap places count 0
Cl
1
and Cl
2
also lie in yz plane, and behave as Si count +1 each
grand total +3
No. of modes of each symmetry species
Example - SiH
2
Cl
2
Point group C
2v
Overall we have:
E C
2
o
v
(xz) o
v
(yz)
+15 -1 +3 +3
This is the reducible representation of the set
of 3N (=15) atomic displacement vectors
We reduce it to the irreducible representations,
using a formula
Character table
C
2v
1E 1C
2
1o
v
(xz) 1o
v
(yz) h = 4
A
1
+1 +1 +1 +1 z x
2
, y
2
, z
2
A
2
+1 +1 -1 -1 R
z
xy
B
1
+1 -1 +1 -1 x, R
y
xz
B
2
+1 -1 -1 +1 y, R
x
yz
Formula is
Reducible representation 15 -1 3 3
No. of A
1
motions = 1/4 [1.15.1 + 1.(-1).1 + 1.3.1 + 1.3.1] = 5
Reduce the reducible representation
Character table
C
2v
1E 1C
2
1o
v
(xz) 1o
v
(yz) h = 4
A
1
+1 +1 +1 +1 z x
2
, y
2
, z
2
A
2
+1 +1 -1 -1 R
z
xy
B
1
+1 -1 +1 -1 x, R
y
xz
B
2
+1 -1 -1 +1 y, R
x
yz
Formula is
Reducible representation 15 -1 3 3
No. of A
1
motions = 1/4 [1.15.1 + 1.(-1).1 + 1.3.1 + 1.3.1] = 5
No. of A
2
motions = 1/4 [1.15.1 + 1.(-1).1 + 1.3.(-1) + 1.3.(-1)] = 2
Character table
C
2v
1E 1C
2
1o
v
(xz) 1o
v
(yz) h = 4
A
1
+1 +1 +1 +1 z x
2
, y
2
, z
2
A
2
+1 +1 -1 -1 R
z
xy
B
1
+1 -1 +1 -1 x, R
y
xz
B
2
+1 -1 -1 +1 y, R
x
yz
Formula is
Reducible representation 15 -1 3 3
No. of A
1
motions = 1/4 [1.15.1 + 1.(-1).1 + 1.3.1 + 1.3.1] = 5
No. of A
2
motions = 1/4 [1.15.1 + 1.(-1).1 + 1.3.(-1) + 1.3.(-1)] = 2
No. of B
1
motions = 1/4 [1.15.1 + 1.(-1).(-1) + 1.3.1 + 1.3.(-1)] = 4
No. of B
2
motions = 1/4 [1.15.1 + 1.(-1).(-1) + 1.3.(-1) + 1.3.1] = 4
Symmetry species of all motions are:-
5A
1
+ 2A
2
+ 4B
1
+ 4B
2
- the irreducible representation
Translations, rotations, vibrations
3 of these are translations of the whole molecule
3 are rotations
Symmetry species of translations are given by
vectors (x, y, z) in the character table
Symmetry species of rotations are given by R
x
,
R
y
and R
z
in the character table
Symmetry species of all motions are:-
5A
1
+ 2A
2
+ 4B
1
+ 4B
2
Character table
C
2v
1E 1C
2
1o
v
(xz) 1o
v
(yz) h = 4
A
1
+1 +1 +1 +1 z x
2
, y
2
, z
2
A
2
+1 +1 -1 -1 R
z
xy
B
1
+1 -1 +1 -1 x, R
y
xz
B
2
+1 -1 -1 +1 y, R
x
yz
Translations are:- A
1
+ B
1
+ B
2
Rotations are:- A
2
+ B
1
+ B
2
- so vibrations are:- 4A
1
+ A
2
+ 2B
1
+ 2B
2
Translations, rotations, vibrations
Symmetry species of vibrations
are:- 4A
1
+ A
2
+ 2B
1
+ 2B
2
Vibrational modes of SiH
2
Cl
2
What does each of these modes look like?
2 rules
(i) there is 1 stretching vibration per bond
(ii) must treat symmetry-related atoms together
Vibrational modes of SiH
2
Cl
2
2 rules
(i) there is 1 stretching vibration per bond
(ii) we must treat symmetry-related atoms together
We therefore have:-
two stretching modes of the SiCl
2
group
two of the SiH
2
group
The remaining five modes must be deformations
(angle bending vibrations)
Vibrational modes of SiH
2
Cl
2
We therefore have:-
two stretching modes of the SiCl
2
group
We can stretch the two Si-Cl bonds
together in phase
or together out of phase
Is vibration symmetrical with
respect to each symmetry
operation?
- if yes +1, if no -1
From the character table,
this belongs to the symmetry
species A
1
We call the mode of vibration
v
sym
SiCl
2
E C
2
o
xz
o
yz
+1 +1 +1 +1
x
z
y
Is vibration symmetrical
with respect to each
symmetry operation?
- if yes +1, if no -1
E C
2
o
xz
o
yz
From the character table,
this belongs to the
symmetry species B
2
We call the mode of
vibration v
asym
SiCl
2
+1 -1 -1 +1
x
z
y
Vibrational modes of SiH
2
Cl
2
We therefore have:-
two stretching modes of the SiCl
2
group
We can stretch the two Si-H bonds
together in phase
or together out of phase
and two stretching modes of the SiH
2
group
x
z
y
From the character table, this
belongs to the symmetry
species A
1
We call the mode of vibration
v
sym
SiH
2
E C
2
o
xz
o
yz
+1 +1 +1 +1
From the character table, this
belongs to the symmetry
species B
1
We call the mode of vibration
v
asym
SiH
2
E C
2
o
xz
o
yz
+1 -1 +1 -1
x
z
y
Vibrational modes of SiH
2
Cl
2
We now have:-
two stretching modes of the SiCl
2
group
two of the SiH
2
group
The remaining five modes must be deformations
(angle bending vibrations)
As with stretches, we must treat symmetry-
related atoms together
From the character table, this
belongs to the symmetry
species A
1
We call the mode of vibration
o
sym
SiCl
2
(or SiCl
2
scissors)
E C
2
o
xz
o
yz
+1 +1 +1 +1
x
z
y
From the character table, this
belongs to the symmetry
species A
1
We call the mode of vibration
o
sym
SiH
2
(or SiH
2
scissors)
+1 +1 +1 +1
E C
2
o
xz
o
yz
x
z
y
From the character table, this
belongs to the symmetry
species B
1
We call the mode of vibration e
SiH
2
(or SiH
2
wag)
E C
2
o
xz
o
yz
+1 -1 +1 -1
x
z
y
From the character table, this
belongs to the symmetry
species B
2
We call the mode of vibration
SiH
2
(or SiH
2
rock)
+1 -1 -1 +1
E C
2
o
xz
o
yz
x
z
y
y
x
From the character table, this
belongs to the symmetry
species A
2
We call the mode of vibration t
SiH
2
(or SiH
2
twist)
E C
2
o
xz
o
yz
+1 +1 -1 -1
Vibrational modes of SiH
2
Cl
2
Overall, we now have:-
two stretching modes of the SiCl
2
group
A
1
+ B
2
two of the SiH
2
group
A
1
+ B
1
five deformation modes
2A
1
+ A
2
+ B
1
+ B
2
Together, these account for all the modes we
expect:
4A
1
+ A
2
+ 2B
1
+ 2B
2
Good Luck In the Final Exam!
Final Exam
Content: Chapters 5-9
Time: J une 13, 8:00-10:00
Venue: -102
Tools:
: J une 10-12,
316()