General contraction of Gaussian basis sets. I. Atomic natural orbitals for first- and second-row atoms

Abstract

A general contraction scheme for Gaussian basis sets is presented. The contraction coefficients are defined by the natural orbitals obtained from an atomic configuration-interaction calculation. Such atomic natural orbitals provide an excellent basis for molecular electronic structure calculations. Large primitive sets can be contracted to only a few functions without significant loss in either the SCF or correlation energy. Polarization functions can be included using the same approach.