Geometry of Molecules. I. Wavefunctions for Some Six- and Eight-Electron Polyhydrides

Abstract

Potential surfaces have been investigated for BH2+, BH2−, NH2+, BeH2, BH3, CH3+, and BeH3− by means of LC (Hartree—Fock) AO MO SCF wavefunctions. One-electron-energy-versus-angle diagrams were determined for these AH2 and AH3 molecules, and comparison with the widely used empirical diagrams of Walsh demonstrates a quantitative similarity between them. In addition, mathematical inequalities are derived relating changes in the sum of one-electron energies with angle to changes in the total energy with angle. Aided by these expressions, we are able to make direct connection between Walsh's qualitative rules and the physically well-defined ab initio solutions.