Exercises

QUESTIONS

1. Define symmetry and symmetry elements.

2. List the distinct operations implied by C6 axis.
3. Define symmetry operation. Mention any two symmetry operations.
4. Define centre of symmetry. Which of the molecules have a centre of
symmetry?
(i) C 6H 6 (ii) CO 2 (iii) SC> 2 (iv) H 20
5. List the symmetry elements present in the following molecules.
(i) NH 3 (ii) CO 2 (iii) BC1 3 (iv) Benzene (v) H 20 (vi) B2H 6 (vii) N 2F2
(viii) PF 5 (ix) Naphthalene (x) CC13Br
6. Define the terms (i) class (ii) subgroup.
7. What are commutative operations?
8. Define the properties of a group.
9. Show that a Sn axis generates 2n operations if n is odd and n operations if n
is even.
10. What is meant by an Abelian group?
11. Evaluate the products av av, and C2 av for a C2v point group.
12. Prove that the Sn axis-is the same as the Cn 12 axis when n is even.
13. Prove that the Sn axis is the same as the C n axis when n is odd.
14. What are conjugate elements?
15. Define order of a group.
16. What is the necessity to include E with all the groups?
17. In C3 and C3v point groups, predict whether C3 and C/ are conjugate
elements.
18. What is an isomorphic group?
19. The presence of C2(x) and C2(y) in a molecule automatically requires the presence
I
I
of C2<z>in the molecule. Why?
I 20. Show that the following commute.(i) Cn and a (ii) a xy and a yz (iii) C2<z> and
I
I
c2 <y>
21. Identify the subgroups of the D 2h point group.
 A SIMPLE APPROACH TO (;ROUP THEORY IN CHEMISTRY

22. List the operations of 511 " when n is odd and when n is even.
23 C " = E but S11 11 :;c E when n is odd. Why?
24: Show that S,, requires the presence of C11 when n is ~dd. .
25 _ What is meant by the terin group? Assign appropriate point groups to the
follm.ving 1nolecules. . .
(i)BC1 (ii) Benzene (iii) C2H 4 (iv)CH4 (v) N:1 3 (v1) H 20~. (czs and trans)
3
(vii) CHCI (viii) SO (ix) H 2S (x) CH 2Cl 2 (x1) HCHO (xn) CH 2=C(Cl) (F)
(xiii) Pyridine (xiv) ~yclohexane (xv) HOCl (xvi) HOD .
(xvii) CIF3 (T-shaped) (xviii) XeF 4 (xix) XeOF 4 (xx) BrF 5 (xx1) Allene
(xxii) C H (xxiii) Ferrocene (staggered and eclipsed) (xxiv) Naphthalene
(xxv) ~t~acene (xxvi) Cyclopentadiene (xxvii) Cis-Pt(NH3)iC12
(xxviii) [Co(enh] 3+ (xxix)HC03-(xxx)S8 (xxxi)SiF 62- (xxxii)C032-
(xxxiii) p-Dichlorobenzene (xxxiv) NaOCl (xxxv) H 2
26. State the conditions that must be obeyed by a set of elements to form a group.
Show that the set of elements 1, -1, i and -i forms a group.
27. What is meant by a similarity transformation? Carry out all possible similarity
transformations on the elements of the C3v point group.
28. Identify the classes and subgroups of the C3v point group.
29. What is meant by matrix representation of a group? Arrive at the matrix
representation for the C2v point group.
30. Give the transformation matrix of (i) E (ii) a xy (iii) Cn(z) (iv)Sn and (v) i
31. Show that S2 = i using the matrix method.
32. Construct the group multiplication table for the C3v point group . .
33. What are reducible and irreducible representations?
34. Explain the block factoring method.
35. Carbon monoxide belongs to the C v point group. Find the irreducible
00

representation that results when symmetry operations of this group are

performed on the z coordinate of the oxygen atom.
36. Reduce the given reducible representation in to its component irreducible
representations of the C2v group.
r=4 2 o 2
37. The character of a reducible representation of a c v group are
2
r=27 -1 1s
Determine how many times each irreducible representation of C is present
. . 2v
rn r·
38. Define character. Construct the C3v character table.
" 39. What is direct product? Give its application.
40. Differentiate direct product and matrix multiplication.
41. State the great orthogonality theorm and give its significance.
42. Obtain the reducible representation for the rt-orbitals in 1,3,-butadiene.
EXERCIS ES
G
43. Hm,v m any irreducible representations are possible for the C and C point
-3v 2v
groups?
44. Find th e representation corresponding to the total number of degrees of
freedom of the water molecule.
45. Find the-direct products of the following for the C2V point group ' A 1 x A 1 A 1 x A2'
1

B1 x B1, B1 x A1, B2 x Az, B2 x B2 ,B1 x B1, Az x A2

46. Find the symmetry of stretching and bending vibrations of the water
molecule.
47. How is group theory used to determine the IR activity of the fundamental
vibrations of a molecule?
48. Discuss the hybridisation schemes for a-orbitals using the tetrahedral molecule
AB 4 and the D 311 AB 5 molecule.
49. Using group theory, how can one predict the infrared and Raman activity or
otherwise of a normal mode of vibration of the NH3 molecule.
50. Show how group theory helps in the prediction of IR activity of the
fundamentals of HCHO.
➔

51. Determine the symmetry of the z and R2 in a C3v symmetrical environment.

➔ ➔

52. Find the symmetry of x and y belonging to a C2v point group.

MULTIPLE CHOICE QUESTIONS

1. Which of the following molecules possesses a centre of symmetry?

a. PtCI4 b . NH3 c. Chlorobenzene (d) pyridine
2. The number of symmetry operations associated with the S4 axis is .
a. 3 b. 6 c. 4 d. 8
3. The point group for the benzene molecule is
a. D2h b. D6h C. c3v d. c2h
4. Pick out the pair of conjugate elements for the C3v point group
a. C3' and C/ b. C3' and a v l c. C/ and 0 v2
d. C/
and a v2
5. The number of symmetry elements for a tetrahedral molecule is
a. 15 b. 24 -"c. 13 d. 20
6. The point group for the ethylene molecule is
a. D2h b. c2h c. c3h d. c4h
7. The symmetry of the symmetric stretching vibration of the water molecule
is
a. A1 b. A 2 c. B2 d. B1
8. The symmetry of the anti-symmetric stretching vibration of the water molecule
is
 • a. A1
A SIMPLE APPROACH TO GROUP THEORY IN CHEMISTRY

9. The bending vibration of the water 1nolecule has the symmetry

b. A 2 c. B2 d . B1
10. The syn1n1etry of the a orbitals of the >C=O group in the C2v point group
111olecule is
a. A 1 b. A 2 c. 8 2 d. B1
yi. The nu1nber of IRs possible for the C3v point group is
a. 4 b. 3 c. 5 d. 1
12. The number of IRs possible for the C2v point group is
a. 4 b. 3 c. 5 d. 1
13. The nun1ber of classes for a C2v point group is
a. 4 b. 3 c. 5 d. 6
1-1. The order for a D311 point group is
a. 12 b. 6 c. 8 d. 4
15. Whicl1 of the following is not a symmetry element of the C3v point group?
a. E b. C3 c. i d. a
16. Which of the following is a symmetry element of the D3h point group?
a. ah b. i c. C4 d. S4
17. The point group of the pyridine molecule is
a. c2v b. c2h C. D3h d. c6
18. Which of the following modes of vibration is IR-inactive for the XeF 4
molecule?
a. A 1 g b. A 2u C. E1u d. B1g
~ - For the NH3 molecule, the IR-active modes of vibration are
a. A 1 and B1 b. A 1 and E c. A 1 and A 2 d. B1 and E
20. For the water molecule, the IR-active modes and Raman-active modes are
a. A 1 and B1 b. A 1 and E c. A 1 and B2 d. B1 and E
21. Which one is not a sub group of the D 2hgroup?
a. c2h b. c2v C. D2 d. 02d
22. The product of the symmetry elements C 2(z) x axz is equal to
a. ayz b. a2(z) C. E d. a xz
23. C2(z) X C2(z)
a · a yz b. C2<z ) c. E d. a xz .
24. The number of symmetry planes present in an AB 6 type octahedral molecule
is
a. 4 b. 3 c. 9 d. 6
25. The number of C2 axes present in an AB 6 type octahedral molecule is
a. 4 b. 3 c. 5 d. 6