Approximate Self-Consistent Molecular Orbital Theory. II. Calculations with Complete Neglect of Differential Overlap

Abstract

The approximate self-consistent molecular orbital method with complete neglect of differential overlap (CNDO), described in Paper I, is used to calculate molecular orbitals for the valence electrons of diatomic and small polyatomic molecules. A small number of bonding parameters (β-resonance integrals) are chosen semiempirically so that the results are comparable to previous accurate LCAO—SCF wavefunctions for diatomic hydrides using a similar basis set. With this calibration, it is found that calculations on other diatomics and polyatomics lead to molecular orbitals and electron distributions in reasonable agreement with the full calculations where available. Although the new method is not yet successful in predicting bond lengths and dissociation energies, it does lead to the correct geometry, reasonable bond angles and bending force constants for the polyatomic molecules considered. It also gives calculated barriers to internal rotation for ethane, methylamine, and methanol which are in fair agreement with experiment.