Molecular Orbital - Quantitative Approach

Quantitative Approach

To obtain quantitative values for the molecular energy levels, one needs to have molecular orbitals that are such that the configuration interaction (CI) expansion converges fast towards the full CI limit. The most common method to obtain such functions is the Hartree–Fock method, which expresses the molecular orbitals as eigenfunctions of the Fock operator. One usually solves this problem by expanding the molecular orbitals as linear combinations of Gaussian functions centered on the atomic nuclei (see linear combination of atomic orbitals and basis set (chemistry)). The equation for the coefficients of these linear combinations is a generalized eigenvalue equation known as the Roothaan equations, which are in fact a particular representation of the Hartree-Fock equation. There are a number of programs in which quantum chemical calculations of MOs can be performed, including Spartan and HyperChem.

Simple accounts often suggest that experimental molecular orbital energies can be obtained by the methods of ultra-violet photoelectron spectroscopy for valence orbitals and X-ray photoelectron spectroscopy for core orbitals. This, however, is incorrect as these experiments measure the ionization energy, the difference in energy between the molecule and one of the ions resulting from the removal of one electron. Ionization energies are linked approximately to orbital energies by Koopmans' theorem. While the agreement between these two values can be close for some molecules, it can be very poor in other cases.