Approximate Self-Consistent Molecular Orbital Theory. I. Invariant Procedures

Abstract

A general discussion of approximate methods for obtaining self-consistent molecular orbitals for all valence electrons of large molecules is presented. It is shown that the procedure of neglecting differential overlap in electron-interaction integrals (familiar in π-electron theory) without further adjustment may lead to results which are not invariant to simple transformations of the atomic orbital basis set such as rotation of axes or replacement of s, p orbitals by hybrids. The behavior of approximate methods in this context is examined in detail and two schemes are found which are invariant to transformations among atomic orbitals on a given atom. One of these (the simpler but more approximate) involves the complete neglect of differential overlap (CNDO) in all basis sets connected by such transformations. The other involves the neglect of diatomic differential overlap (NDDO) only, that is only products of orbitals on different atoms being neglected in the electron-repulsion integrals.