Self-Consistent Molecular Orbital Methods. IV. Use of Gaussian Expansions of Slater-Type Orbitals. Extension to Second-Row Molecules

Abstract

Least‐squares representations of the $\text{3s}$ and $\text{3p}$ Slater‐type atomic orbitals by a small number of Gaussian functions are presented. The use of these Gaussian representations in self‐consistent molecular orbital calculations extends our previous study to molecules containing second row elements. Calculated atomization energies, electric dipole moments, and atomic charges are shown to rapidly converge (with increasing number of Gaussians) to their Slater limits. Results of valence shell optimization studies on a series of second‐row compounds are nearly independent of the level of the Gaussian approximation, and they allow a set of standard molecular $\xi$ exponents to be proposed.