Quantum Chemistry II – Molecular Symmetry

Abhinav Senthil
16. 1 Can a molecule with an inversion center have a dipole moment? Give an example of a
molecule with this symmetry element and explain your reasoning.

A molecule with a center of inversion i can not have a net dipole moment. For a net dipole moment
to exist, there must be an asymmetric distribution of charge on the molecule. Consider
buckminsterfullerene. Any arbitrary point in 3-dimension space of nature (x, y, z) gets mapped onto
its corresponding symmetric point (-x, -y, -z) by the inversion center. This cannot be possible if an
asymmetric element in the molecule exists to give rise to an uneven charge distribution.

16.3 Why does the list of elements for the D6h group in Table 16.2 not list the elements C 62, C63, and
C64?

The Cnm symbol denotes a rotation around an axis by an angle given by 360/n, up to m times. It
naturally follows that m ≤ n. In general, these rotations are expressed in their simplest fractions m/n,
so the C62 is denoted by C3, C63 is denoted as C2 and C64 is denoted by C32, which are all symmetry
elements found within the D6h group.

16.3 Use the logic diagram of Figure 16.2 to determine the point group for the planar molecule
trans-HBrC=CBrH. Indicate your decision-making process as was done in the text for NH 3.

Starting from the top of the flowchart, our compound trans-1,2 dibromo ethene is not linear. The
molecule has a singular C2 axis as well as a mirror plane. The C 2 axis and mirror plane are
perpendicular so the point group of trans-1,2 dibromo ethene is C 2h.

16.4 The D3 group has the following classes: E, 2C 3, and 3C2. How many irreducible representations
does this group have and what is the dimensionality of each?

Counting up the elements of the D3 group, we have E, two C3 axes and three C2 axes for a total of 6
elements. These 6 elements are comprised of 3 classes (E, C 2 and C3) so there are 3 irreducible
representations. We the consider d12 + d22 + d32 = h = 6.

The only solution that exists is given by 2 one dimensional representations and 1 two dimensional
representation (22 + 12 + 12 = 6).