CHM 6V39

Basis Set Exercises

Due Feb. 17, 2005

You are to calculate the Hartree-Fock equilibrium geometry, the total energy, the orbitals, and the ionization potential for both HCl and ethylene using a variety of basis sets. Tabulate the H-Cl distance, the total energy, and the ionization potential (= -E for the highest occupied MO [HOMO] by Koopman’s theorem) for HCl. Make a similar table for ethylene, where there are more relevant geometries: the H-C-H angle, the H-C-C angle, the C-H distance, and the C=C distance. Obtain the experimental geometries and ionization potentials from the literature, and report them too for comparison.

Basis sets to use are:

STO-3G
3-21G*
6-31G*
6-31G**
6-31+G**

Review your orbitals in each case and show that the number of basis functions is as expected, given the description of the basis set in Hehre. Describe the HOMO in each case. Note that for HCl there are two degenerate (energetically identical) HOMOs.