Chapter 3: Symmetry and Group Theory

Week 6-1

Group Theory is used to understand spectroscopic results of inorganic complexes, IR, Electronic spectroscopy, etc. Group theory uses symmetry, so you dont have to do MATH!! Yeah!! How do we use symmetry? First off, we need to visualize symmetry, which of these shapes are symmetrical?

Now we need to develop a vocabulary to discuss symmetry. Mirror Planes Rotational Axis Improper Rotational Axis. With these three functions, we can assign a symmetry group (Point Group) to any molecule we find. Mirror Planes

Rotational Axis
Week 6-2

Improper Rotations;

Rotational axis and Mirror plane

Week 6-3

Once the Molecule has a Point group, then that will help us assign the symmetry of d-orbitals for electronic spectra and vibrations for IR, etc.

This is very powerful since we will never use a mathematical equation to do this. Now, how do we use these methods to assign a Point group to a molecule?

This Flow chart will be given to you in the exam, and you will be required to assign the Point group.

Examples:
Week 6-4

Once the Point group is assigned, now we can really get down to business by looking at the Character Table. This Table will be given to you in the exam but you MUST know how to use it. Each Table can be broken up into Irreducible Representations. These are the horizontal rows of A, B, E, T etc.

Note that the Eg irreducible Rep. is a doublet (E=2) and that these terms are in the MO diagram of Sq. Planar. Now how can we use these character tables to help us?
Week 6-5

Optical Activity or Chirality: Is it or not? Inorganic complexes are more complicated than simple organic compounds so there are more examples of lack of symmetry.

You will only see optical activity if the complex is asymmetric or dissymmetric. Electronic Spectra: Depends on a change in the Dipole moment. This will be discussed in more detail next week (Ch. 11) but for now, molecules with centers of inversion cannot generate a change in their dipole. Hence the transitions are symmetry forbidden. IR Spectroscopy: For a particular vibration to be detected by IR, there must be a change in the dipole moment. N2 has a center of inversion, so there is no change in dipole, IR in-active.

CO does not have an i, so there is a change in the dipole, IR active. H2O is more complicated, so it is harder to determine.
Week 6-6

However, if you know the vibration that is happening (this will be given to you in an exam), you can assign it to be IR active or not by looking at the character table.

All vibrations that have symmetry that corresponds to x, y, or z vectors will be IR active. See C2v Table.

This same concept was used to determine the structure of XeF4. Is it sq. planar or Td? The IR bands are at 123, 291, and 586 cm-1. The Raman bands are at 502, 543, 235 cm-1. Note that the 221 cm-1 band is due to an overtone, so not a pure stretch or bend. This data proves XeF4 is sq. planar because if it was Td then the IR and Raman bands would have the same energy.

Bonding: These concepts can also be applied to bonding and the symmetry overlap of LGOs and d-orbitals.

In closing, you can see that by having these character tables we do not have to calculate whether orbitals overlap because the symmetry will tell us. We did not discuss how these stretching/bending modes or LGOs are determined in the first place because this is out of the scope of this class.
Week 6-7

However, it does include further use of the character tables and mathematical calculations.