Linear augmented-Slater-type-orbital method for electronic-structure calculations

Abstract

The purpose of this paper is to explore the possibility of using augmented Slater-type orbitals (STO) as basis functions for electronic-structure calculations. STO's have a radial dependence given by ${r}^{n\ensuremath{-}1}\mathrm{exp}(\ensuremath{-}\ensuremath{\zeta}r)$ and as a result have a number of important advantages. They are localized about sites and have the same asymptotic form as actual atomic orbitals. They are regular at the origin and possess analytic Fourier transforms. The Fourier transform can be manipulated to yield an addition theorem, that is, a reexpansion formula for an STO about another site which is similar to the one used for spherical Bessel functions. Augmenting the STO's with numerical solutions of the Schr\"odinger equation within touching spheres leads to a small secular matrix since the numerical functions are orthogonal to all the core states and the STO's are only used in the interstitial region. The method has been applied to copper, silver, and palladium using Chodorow-type potentials and accounting for all relativistic effects except spin-orbit coupling. The results on copper are in good agreement with previous calculations and with experiments. The results on Pd and Ag are in better agreement with photoemission experiments than fully self-consistent local-density calculations.