Name: Solutions

Due date: 11/07/03

Some general comments: The number of elements of symmetry is not the same as the number of symmetry operations. (Recall that a symmetry element can be associated with more than one symmetry operation). The total number of symmetry operations gives the order of the group and not the total number of elements of symmetry. The order of a group (total number of symmetry operations) will always be an even number. It cannot be an odd number. The total number of elements of symmetry can be either an even or an odd number. Try to identify elements of symmetry such that equivalent positions (atoms or groups) will be interchanged as the result of the symmetry operation. When identifying an axis of symmetry to be an element of symmetry (or not), also check the other two axes that are orthogonal to it. When identifying a plane of symmetry (reflection plane) to be an element of symmetry (or not), also check the other two planes that are orthogonal to it.

Name: Solutions

Due date: 11/07/03

1. List the various symmetry elements for each of the molecules below, determine what group the molecule belongs to, and determine what is the order of that group. A) SO 3 (trigonal planar)

O O S O
B) CH 4

Symmetry elements: E, C3, 3C2, h, S3, 3v Point group: D3h Order of the group: 12

H H
C) C 6 H 6

Symmetry elements: E, 4C3, 3C2, 3S4, 6d

Point group: Td Order of the group: 24

Symmetry elements: E, C6, 3C2, i, S6, h, 3v, 3d Point group: D6h Order of the group: 24 D) ortho-dichlorobenzene

Cl Cl
E) meta-dichlorobenzene

Symmetry elements: E, C2, 2v Point group: C2v Order of the group: 4

Cl

Cl

Symmetry elements: E, C2, 2v Point group: C2v Order of the group: 4

F) para-dichlorobenzene Symmetry elements: E, 3C2, i, 3v

Cl

Cl

Point group: D2h Order of the group: 8

2. List the various symmetry elements for each of the molecules below, determine what group the molecule belongs to, and determine what is the order of that group. A) cis - CHBr = CHBr Symmetry elements: E, C2, 2v Point group: C2v Order of the group: 4

Br H

Br H

B) trans - CHCl = CHCl

Cl H

H Cl

Symmetry elements: E, C2, i, h Point group: C2h Order of the group: 4

C) chloroform ( CHCl 3 )

H Cl Cl Cl

Symmetry elements: E, C3, 3v Point group: C3v Order of the group: 6

D) naphthalene ( C10 H 8 ) Symmetry elements: E, 3C2, i, 3v Point group: D2h Order of the group: 8 E) anthracene ( C14 H10 ) Symmetry elements: E, 3C2, i, 3v Point group: D2h Order of the group: 8 F) XeF4 (square planar)

Symmetry elements: E, C4, 4C2, i, S4, h, 2v, 2d Point group: D4h Order of the group: 16

Xe F F

3. Show that R x (a vectorial representation of the rotation around the x axis) forms a basis for the irreducible representation B 2 of the point group C 2v . Solution: The two vectors representing the rotation around the x axis are represented in red in the figure on the right. Those vectors are symmetric with respect to identity operation, antisymmetric with respect to rotation around the z axis ( C 2 axis), antisymmetric with respect to reflection in xz ( v ), and symmetric with respect to reflection in yz ( v ).

y x

Comparing with the C 2v character table, the R x (the vectors representing rotation around x axis) is a basis of B 2 .

4.

Show that the rows of the character table of C 2 h satisfy

classes

n( R) i ( R) j ( R) = h ij .

Solution: The character table of C 2 h : C 2h

E
1 1 1 1

C2 1 1 1 1

h 1 1 1 1
Rz

Ag

1 1 1 1

x 2 , y 2 , z 2 , xy
xz , yz

Bg Au Bu

Rx , R y z x, y

The order of the group is h = 4 . First consider the cases where i=j, where the sum should give a value of 4: ( R) ( R) = 1 + 1 + 1 + 1 = 4
R Ag Ag

B
R R

( R ) Bg ( R ) = 1 + 1 + 1 + 1 = 4
u

A ( R) A
u

( R) = 1 + 1 + 1 + 1 = 4

B
R

( R) Bu ( R) = 1 + 1 + 1 + 1 = 4

Now consider the cases where i j , where the sum should give a value of 0:

A
R R

( R ) Bg ( R ) = 1 1 + 1 1 = 0 ( R) Au ( R ) = 1 + 1 1 1 = 0 ( R) Bu ( R) = 1 1 1 + 1 = 0 ( R) Au ( R) = 1 1 1 + 1 = 0 ( R) Bu ( R ) = 1 + 1 1 1 = 0
u

A A
R

B
R

B
R R

A ( R) B
u

( R) = 1 1 + 1 1 = 0

5.

Suppose the characters of a reducible representation of the Td point group are X (E) = 17, X (C ) = 2, X (C ) = 5, X (S ) = 3, and X ( ) = 5, or = 17 2 5 3 5 .
3 2 4 d

Determine how many times each irreducible representation of Td is contained in .

Solution:
1 n( R) ( R) i ( R) h classes

Use ai =

1 [17 + 8(2) + 3(5) + 6(3) + 6(5)] = 0 24 1 a A2 = [17 + 8(2) + 3(5) 6(3) 6(5)] = 4 24 1 a E = [2(17) 8(2) + 3(2)(5) + 0 + 0] = 2 24 1 aT1 = [3(17) + 0 3(5) + 6(3) 6(5)] = 2 24 1 aT2 = [3(17) + 0 3(5) 6(3) + 6(5)] = 1 24 a A1 = = 4 A2 + 2 E + 2T1 + T2

6.

Suppose the characters of a reducible representation of the D 3h point group are

= 12 0 2 4 2 2 . Determine how many times each irreducible representation of D 3h is contained in .

Solution:
1 n( R) ( R) i ( R) h classes

Use ai =

a A' =
1

a A'

aE' a A''
1

a A''

a E ''

1 [12 + 2(0) + 3(2) + 4 + 2(2) + 3(2)] = 1 12 1 = [12 + 2(0) 3(2) + 4 + 2(2) 3(2)] = 1 12 1 = [2(12) + 0 + 0 + 2(4) 2(2) + 0] = 3 12 1 = [12 + 2(0) + 3(2) 4 2(2) 3(2)] = 0 12 1 = [12 + 2(0) 3(2) 4 2(2) + 3(2)] = 2 12 1 = [2(12) + 0 + 0 2(4) + 2(2) + 0] = 1 12

' ' ' = A1 + A2 + 3E ' + 2 A2' + E ''

7.

Show that the molecular orbital 2 =

1 6

( 1 2 + 3 4 + 5 6 ) in benzene

belongs to the irreducible representation B2g .

Solution:

The 2 is represented like:

This orbital is: symmetric with respect to E

antisymmetric with respect to C 6 (axis perpendicular to the plane of the molecule) symmetric with respect to C3 (axis perpendicular to the plane of the molecule)

antisymmetric with respect to C 2 (axis perpendicular to the plane of the molecule) antisymmetric with respect to C 2 (axes going through two opposite carbon atoms) symmetric with respect to C 2 (axes going through the middle of two opposite bonds)
symmetric with respect to i antisymmetric with respect to S 3 symmetric with respect to S 6

antisymmetric with respect to h (the plane of the molecule) antisymmetric with respect to d (planes perpendicular to the plane of the molecule and going through the middle of two opposite bonds) symmetric with respect to v (planes perpendicular to the plane of the molecule and going through two opposite carbon atoms) This orbital transform like the irreducible representation B2g therefore it belongs to the irreducible representation B2g .

8.

Using 2 = 1

1 6

( 1 2 + 3 4 + 5 6 ) and

3 =

(2 1 + 2 3 2 4 5 + 6 ) molecular orbitals in benzene determine H 22 , H 33 , 12 H 32 , and H 23 .

Solution:

Recall that the Hckel molecular-orbital theory sets the Coulomb integrals to be , the overlap integrals to be S ij = ij , and the resonance integrals involving the 2 p z orbitals of nearestneighbor carbon atoms to be . Also recall that the j ' s that comprise the j molecular orbitals are the 2 p z orbitals centered on the individual carbon atoms. Thus
6 6 1 6 * H 22 = 2 H 2 d = * H j d + i* H i d = j 6 j =1 i =1 i j j =1 1 * * * * * * = ( 1 H 1d 1 H 2 d + 1 H 3 d 1 H 4 d + 1 H 5 d 1 H 6 d 6 * H d + * H d * H d + * H d * H d + * H d

2 1 2 2 2 3 2 4 2 5 2 6 * * * * * * + 3 H 1d 3 H 2 d + 3 H 3 d 3 H 4 d + 3 H 5 d 3 H 6 d * * * * * * 4 H 1d + 4 H 2 d 4 H 3 d + 4 H 4 d 4 H 5 d + 4 H 6 d * * * * * * + 5 H 1d 5 H 2 d + 5 H 3 d 5 H 4 d + 5 H 5 d 5 H 6 d * * * * * * 6 H 1d + 6 H 2 d 6 H 3 d + 6 H 4 d 6 H 5 d + 6 H 6 d )

1 ( + 0 0 + 0 6 + + 0 0+ 0 + 0 + + 0 0 0 + 0 + + 0 + 0 0 + 0 + + 0 0 + 0 +)

1 (6 12 ) = 2 6 Similarly H 33 = + , H 23 = 0 , and H 32 = 0 .

9. Show that if we used a 2 p z orbital on each carbon atom as the basis for a (reducible) representation for benzene, ( D 6 h ) then = 6 0 0 0 2 0 0 0 0 6 0 2 .

Reduce into its component irreducible representations. What does your answer tell you about the expected Hckel secular determinant?
Solution:

The operator E leaves all six 2 p z orbitals unchanged (a reducible character of 6). ' C 2 moves four of the six p-orbitals from one atom to another atom (contributing 0 to the reducible character) and inverts the two remaining p-orbitals (contributing 2 to the reducible character). h inverts all six p-orbitals (a reducible character of 6). v leaves two p-orbitals unchanged (contributing 2 to the reducible character) and moves four porbitals between atoms (contributing 0 to the reducible character). All of the other operators move the orbitals from one atom to another, and so have a reducible character of 0. This gives the representation = 6 0 0 0 2 0 0 0 0 6 0 2 from above. Find that the only nonzero values of ai occur for:

a A2u = a B2 g a E1g a E2 u

1 (6 + 6 + 6 + 6) = 1 24 1 = (6 + 6 + 6 + 6) = 1 24 1 = (12 + 0 + 12 + 0) = 1 24 1 = (12 + 0 + 12 + 0) = 1 24

This result shows that the secular determinant can be written in diagonal form, which when expanded will be the product of two 2 2 determinants (corresponding to the E1g and E 2u

representations) and two 1 1 determinants (corresponding to the A2u and B2 g representations).

10. Propose a question (or more) in the same format as the ones in the exam (one question and five multiple-choice answers) covering the material in the Molecular Symmetry and Group Theory handout (Chapter 12 in the textbook).

Question:

Answers: A) B) C) D) E)