INDIAN INSTITUTE OF TECHNOLY, KHARAGPUR

DEPARTMENT OF CHEMISTRY

Long Test 2 : 2021 Sub. No. : CY41007 Time : 80 mins. F. M. : 20

Subject : GROUP THEORY FOR CHEMISTS

Name: Roll No. :

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Answer all questions

1. i) Write down the projection operator of the most symmetric IR (irreducible

representation) of tetraphenyl methane molecule? [1.5]

ii) Write down the number of irreducible representations (IRs) present in 1,3-dichloro-
2,4 dibromo cyclobutane molecule mentioning the point group. Write down also their
dimensionality and term symbols for the IRs. [2]

iii) Find out the characters of different elements of two un-symmetric IRs of
cis-[Co(en)2Cl2]+ molecule mentioning the underlying principle. [2]

iv) The character of certain elements of a point group in an IR is as follows:

E 2C3 3C2 i 2S6 3d
1 1 -1 -1 -1 1
Identify the point group and the symbol of the IR. Comment on the dipole moment of this
point symmetry group. [2]

v) Which characters does the py orbital of oxygen have in water and what is the
name of this representation? [1.5]
vi) How many doubly degenerate pair of orbitals present in the following molecules Allene,
staggered ethane and S8 ? Justify your answer. [2]

2. i) Fill in the following blanks with suitable words:

g ® g transitions are electric dipole ________ but magnetic dipole _______ whereas g ®
u transitions are electric dipole ________ but magnetic dipole _________ for a
______________ molecule. [1.5]

ii) The second order polarisabilty ((2)) of a centro symmetric system can be written
 as follows :
i e. r m m e. r n n e. r i
 ( 2 )   m ,n
( mi   )( ni  2 )
where i, m and n represent the initial, intermediate and final state respectively and e.r
is the dipolemoment vector. Find the value of (2) and justify your answer. [2]

iii) Find the matrix representation of C3 of the D3h point group in the direct product
space of the two basis set (e1,e2) and (l1 and l2) [1.5]

De(C3) = (−1√3/2/2 −√ 3/2

−1/2 ) Dl(C3) = (01 −1
−1 )

3. Write down the correct option (s) (A/B/C/D) in your answer script. [1x4=4]
i) For acetone molecule, the electronic transition from the ground state to the an
excited state of B2 symmetry is (See the Character Table at the end of the
question)
A) NOT allowed B) allowed with x-polarization C) allowed with y-
polarization D) allowed with z-polarization

ii) The pair of symmetry point groups that are associated with only polar
molecule is
A) C3v, D∞h B) C4v, C2h C) D5h, Td D) C3v, C∞v

iii) The IRs of C2h point group are Ag, Bg, Au, Bu. The Raman active mode of the
trans1,2 dichloro ethylene and trans 1,3-butadienne both belongs to the
irreducible representations
A) Ag, Bu B) Au, Bu C) Au, Bg D) Ag, Bg

iv)
A)
(B)
(C)
(D)

****The End *****

Character table for C2v point group

linear,
E C2 (z) σv(xz) σv(yz) quadratic
rotations
A1 1 1 1 1 z x2, y2, z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz