Calculation of STOs electron repulsion integrals by ellipsoidal expansion and large-order approximations

TL;DR

This paper introduces a systematic method using ellipsoidal expansion and large-order approximations to efficiently compute two-electron integrals over Slater-type orbitals, improving convergence and computational stability.

Contribution

It presents a new approach for calculating higher-order terms in the Neumann series for STO integrals, enhancing efficiency and stability.

Findings

Method improves convergence speed of STO integrals

Analytical expressions facilitate implementation

Enhances stability and efficiency of calculations

Abstract

For general two-electron two-centre integrals over Slater-type orbitals (STOs), the use of the Neumann expansion for the Coulomb interaction potential yields infinite series in terms of few basic functions. In many important cases the number of terms necessary to achieve convergence by a straightforward summation is large and one is forced to calculate the basic integrals of high order. We present a systematic approach to calculation of the higher-order terms in the Neumann series by large-order expansions of the basic integrals. The final expressions are shown to be transparent and straightforward to implement, and all auxiliary quantities can be calculated analytically. Moreover, numerical stability and computational efficiency are also discussed. Results of the present work can be used to speed up calculations of the STOs integral files, but also to study convergence of the Neumann expansion and develop appropriate convergence accelerators.