Constructing the Character Table for C4v

Symmetry Operations grouped by class:

Mulliken Notation:
Symbols for the Irreducible Representations (ΓI)

A – 1 dimensional representation sym. to rotation about Cn

B – 1 dimensional representation antisym. to rotation about Cn
E – 2 dimensional representations
T – 3 dimensional representations

Subscripts: 1 – representation is symmetric to ⊥ C2 (or to σv)

2 – representation is antisym. to ⊥ C2 (or to σv)
g – representation is symmetric to inversion
u – representation is antisym. to inversion

Superscripts: ′ - representation is symmetric to σh

′′ - representation is antisym. to σh
Character Tables and Bonding

We can use character tables to determine the orbitals involved in bonding in

a molecule. This process is done a few easy steps.

1. Determine the point group of the molecule.

2. Determine the Reducible Representation, Γ, for the type of
bonding you wish to describe (e.g. σ, π). Picking the correct basis set
is critical! The Reducible Representation indicates how the bonds
are affected by the symmetry elements present in the point group.
3. Identify the Irreducible Representations that provides the
Reducible Representation; there is a simple equation to do this. The
Irreducible Representation (e.g. 2A1+ B1+ B2) is the combination of
symmetry representations in the point group that sum to give the
Reducible Representation.
4. Identify which orbitals are involved from the Irreducible
Representation and the character table.
I. CH4: Td
MSGT Application: Find ΓR for the σ Bonds in Methane

Td E 8C3 3C2 6S4 6σd

I. CH4: Td
Reduce ΓR for Methane
General Procedure to Get Molecular Orbital Diagram
(for cental atom + ligands)

1. Assign the Point Group and use the appropriate ligand

atomic orbitals to find ΓR, express as sum of ΓI, interpret the
results (using steps on the previous slide).

2. Classify the central atom atomic orbitals according to the ΓI’s

in the character table.

3. Combine central atom atomic orbitals and ligand LCAOs

having the same symmetry
→This will lead to a molecular orbital diagram
I. CH4: Td
I. CH4: Td
II. H2O: C2v
II. H2O: C2v
II. H2O: C2v
II. H2O: C2v
II. H2O: C2v
II. H2O: C2v
III. BF3: D3h
III. BF3: D3h
III. BF3: D3h