CHM301/641 Solutions to Quiz1 on Sep 1, 2016

1. Visual Inspection tells us that column 1 elements repeat in column 5 (similarly row 1 &5). Therefore
Q is the identity as multiplication with Q leaves the element unchanged.
Next we must find which elements multiply to yield Q. It is easy to see that
MP=PM=Q (M=P-1 or P=M-1)
NN=Q (N=N-1)
RR=Q (R=R-1)
SS=Q (S=S-1)
For elements to belong to the same class, they must be conjugate to each other.
Applying similarity transformation and substituting the products from GMT:
M-1PM=P
N-1PN=NR=M (We can already see that M and P are in the same class but you may continue)
R-1PR=RS=M
S-1PS=SN=M
Therefore, M and P are conjugate to each other and are in the same class.
Similarly,
M-1NM=PR=S
P-1NP=MS=R (We can already see that N, R and S are in the same class)
R-1NR=RM=S
S-1NS=SP=R
As Q is always a class in itself, we have three classes of order 1 (Q), order 2 (M,P) and order 3(N,R,S)
2. First step is to identify the order of the group: D2d=4n=8; C4v=2n=8; D4=2n=8.
Next all the symmetry operations should be combined into classes.
D2d = E, 2S4, C2, 22 , 2d (total 5 classes)

C4v = E, 2C4, C2, 2v, 2d (total 5 classes)

D4 = E, 2C4, C2, 22 , 22 (total 5 classes)

In the above arrangement of operations (with order of classes 1, 2, 1, 2, 2 for all three point groups
and that the groups are all of order 8), it doesnt take much time to realize that their irreducible
representations (IRRs) have to be identical. Therefore, it is sufficient to work out the characters for
IRRs for any group you are comfortable with, and then generalize it to the other two. We have
already worked out D4 in the class. Just for revision, lets take C4v.
The total number of IRRs must be equal to the number of classes in the group (=5).
The sum of square of dimensions for IRRs should be equal to the order of the group. Therefore, only
possibility for the dimensions are 1,1,1,1,2.
Also there exists a perfectly symmetric representation so partial character table can be written as
C4v
1
2
3
4
5

E
1
1
1
1
2

2C4
1

C2
1

2v
1

2d
1

2 4 can have only 1 and -1 as characters, at the same time they must be orthogonal to 1. There can
be only 3 orthogonal vectors to 1 which represent 2, 3, 4.
C4v
1
2
3
4
5

E
1
1
1
1
2

2C4
1
1
-1
-1
p

C2
1
1
1
1
q

2v
1
-1
1
-1
r

2d
1
-1
-1
1
s

The values of p, q, r & s can be derived by writing four linear equations obtained by orthogonality
requirement of 5 to 1 4 which yields the following character table and assignment of Mulliken
symbols
C4v
A1
A2
B1
B2
E

E
1
1
1
1
2

2C4
1
1
-1
-1
0

C2
1
1
1
1
-2

2v
1
-1
1
-1
0

2d
1
-1
-1
1
0

Also, from our previous argument, the other two character tables can be written as following.
D2d
A1
A2
B1
B2
E

D4
A1
A2
B1
B2
E

E
1
1
1
1
2

E
1
1
1
1
2

2S4
1
1
-1
-1
0

C2
1
1
1
1
-2

22
1
-1
1
-1
0

2d
1
-1
-1
1
0

2C4
1
1
-1
-1
0

C2
1
1
1
1
-2

22

22

1
-1
1
-1
0

(Note the assignment of B1 and B2 for D2d character table.)

1
-1
-1
1
0

Now we need to consider transformation of unit vector along z axis (pz orbital). It is not difficult to
realize that for C4v all operations leave the vector as is. Therefore z has A1 symmetry.
For D2d: both S4 and 2 will cause inversion implying B2 symmetry

For D4: Only 2 will change orientation of z to z implying A2 symmetry.

3. Very trivial arithmetic operations yield the following.
r1 = A1g+B1g+Eu;

r1 = Eg+A2u+B2u

4. (i) C3h (ii) C2v (iii) C2v (iv) D2h (v) D2d