Self-Consistent Molecular Orbital Methods. VI. Energy Optimized Gaussian Atomic Orbitals

Abstract

Minimal basis atomic orbitals expressed as sums of N Gaussian functions are presented for hydrogen and for the first row atoms boron to fluorine. The expansion coefficients and Gaussian exponents are determined by minimizing the total calculated energy of the atomic ground state. For expansion lengths of up to six Gaussians, two sets of atomic orbitals are reported. In the first set, which we describe as unconstrained, different Gaussian exponents are used for the 2s and 2p atomic orbitals. In the second set, the 2s and 2p atomic orbitals are constrained to share the same Gaussian exponents. It is shown that this constraint, which produces a significant gain in computational speed in molecular calculations, does not seriously reduce the quality of the atomic orbitals for given N . A comparison of the contracted sets presented here with previous studies on uncontracted basis sets for the first row atoms, shows that the uncontracted Gaussian exponents are a poor approximation to those of the contracted functions.