Double Exponential Transformation For Computing Three-Centre Nuclear Attraction Integrals

TL;DR

This paper introduces a double exponential transformation method to efficiently and accurately compute three-centre nuclear attraction integrals, crucial for large molecular electronic structure calculations, by transforming oscillatory integrals into more manageable forms.

Contribution

The paper develops a novel double exponential transformation approach that significantly improves the efficiency and accuracy of evaluating three-centre nuclear attraction integrals in quantum chemistry.

Findings

Achieves high accuracy with reduced computation time

Demonstrates fast convergence in numerical tests

Facilitates large-scale molecular calculations

Abstract

Three-centre nuclear attraction integrals, which arise in density functional and \textit{ab initio} calculations, are one of the most time-consuming computations involved in molecular electronic structure calculations. Even for relatively small systems, millions of these laborious calculations need to be executed. Highly efficient and accurate methods for evaluating molecular integrals are therefore all the more vital in order to perform the calculations necessary for large systems. When using a basis set of $B$ functions, an analytical expression for the three-centre nuclear attraction integrals can be derived via the Fourier transform method. However, due to the presence of the highly oscillatory semi-infinite spherical Bessel integral, the analytical expression still remains problematic. By applying the $S$ transformation, the spherical Bessel integral can be converted into a much more favorable sine integral. In the present work, we then apply two types of double exponential transformations to the resulting sine integral, which leads to a highly efficient and accurate quadrature formulae. This method facilitates the approximation of the molecular integrals to a high predetermined accuracy, while still keeping the calculation times low. The fast convergence properties analyzed in the numerical section illustrate the advantages of the method.