Molecular Spectroscopy and Group Theory

Home Assignment-I

Due date: 19th August 2016

1. For the following molecules, locate all the symmetry elements asociated with them and hence,
deduce their respective point groups.
(a) IF3 O2 (all isomers)
(b) cis[Co(en)2 Cl2 ]
(c) Cubane (C8 H8 )
(d) mer-triamminetrichlorocobalt(III)
(e) Staggered and eclipsed ferrocene (C10 H10 Fe)
2. Figure 1 shows NH3 molecule placed unconventionally in the cartesian coordinate system. In
this coordinate system, the x -axis is the three-fold axis. One of the planes, b makes an
angle of 45 with the y-axis. By considering the transformation of a general point in space,
deduce the six 3 3 matrices which form a set of reducible representations for the C3v point
group.

Figure 1: NH3 molecule

3. Draw all geometrical isomers of [Co(trien)Cl2 ]+ , where trien is the tetradentate ligand triethylenetetramine. Ignore the conformation of chelate rings, identify the symmetry point
group of each isomer and predict whether it is optically active or not.
4. Construct the group multiplication table for C4v point group.
5. Consider the group D3 . Let the C3 axis coincide with the z -axis and one of the C2 axes coincide
with the x -axis. Write out the complete matrices for all the irreducible representations of
this group. Derive from these the character table.

Molecular Spectroscopy and Group Theory

Home Assignment-I

6. [InCl5 ]2- anion (Figure 2) has C4v symmetry. Of the four vertical mirror planes, one v is in the
xy-plane, the other v is in the yz -plane, and the two d s lie in between them. With reference
to the coordinate system based on the orthonormal base vectors e1 , e2 , and e3 (pointing in
the x -, y-, and z -directions, respectively), write down all eight matrices that represent the
symmetry operations of the C4v group. Deduce the character of e , the representation based
on e1 , e2 , e3 . Reduce e to the irreducible representations of C4v .

Figure 2: [InCl5 ]2- molecule