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

TLDR: In this paper, the 3s and 3p Slater-type atomic orbitals are represented by a small number of Gaussian functions and the use of these Gaussian representations in self-consistent molecular orbital calculations is presented.

Abstract: Least‐squares representations of the 3s and 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 ξ exponents to be proposed.