Spherical-harmonic-analysis-based optimization of atomic weighting functions for multicenter numerical integration in molecules

TL;DR

This paper introduces optimized spherical harmonic-based atomic weighting functions for molecular integration, improving efficiency and accuracy in electronic structure calculations through novel function forms and optimized radial schemes.

Contribution

It develops new spherical symmetric weighting functions and optimized radial integration schemes, enhancing the efficiency of molecular integral calculations in electronic structure theory.

Findings

New weighting functions reduce quadrature points needed for accuracy.

Optimized radial double exponential integration scheme improves efficiency.

Validated approach on a set of molecules with controlled accuracy.

Abstract

The well-known spatial integration schemes in molecular electronic structure theory, immune to cusps and point singularities of some kind at atomic positions, use a set of weighting functions to split the integrand into a sum of atom-centered parts, each dealt with in its own spherical coordinate system. Here, for a given set of integrands in the two-center case, a quality measure of the weighting functions is defined to compare, design, and optimize them, it is roughly proportional to the average number of angular quadrature points needed to reach a given integration accuracy. A study of Becke's fuzzy Vorono\"i cells has helped to improve their performance by a new modification. New spherically-symmetric unnormalized weighting functions are found in the form of a negative power times the negative exponential of the fourth power of the scaled distance to the atomic center, with the parameters related to the asymptotic decay of the integrand and the integration accuracy -- these are much simpler but no less efficient and naturally fit for linear-scaling calculations. Radial distribution of spherical quadrature orders is studied. A radial integration scheme of double exponential type is optimized. A symmetric analog of the pseudospectral approximation is used for the seminumerical evaluation of two-electron repulsion integrals. Taken together, this allows efficient calculation of all molecular integrals with well-controlled accuracy, as shown by tests on a set of molecules.