Cholesky decomposition of complex two-electron integrals over GIAOs: Efficient MP2 computations for large molecules in strong magnetic fields

TL;DR

This paper introduces a Cholesky decomposition approach for complex electron-repulsion integrals in large molecules under strong magnetic fields, significantly improving computational efficiency in quantum chemistry calculations.

Contribution

The authors developed and implemented a Cholesky decomposition method for complex ERIs over GIAOs, enabling efficient MP2 computations for large molecules in magnetic fields with rigorous error control.

Findings

Cholesky decomposition achieves effective compression of complex ERIs.

The method allows MP2 calculations on systems with over 2000 basis functions.

Significant reduction in computational time for large-scale magnetic field calculations.

Abstract

In large-scale quantum-chemical calculations the electron-repulsion integral (ERI) tensor rapidly becomes the bottleneck in terms of memory and disk space. When an external finite magnetic field is employed, this problem becomes even more pronounced because of the reduced permutational symmetry and the need to work with complex integrals and wave-function parameters. One way to alleviate the problem is to employ a Cholesky decomposition (CD) to the complex ERIs over gauge-including atomic orbitals. The CD scheme establishes favourable compression rates by selectively discarding linearly dependent product densities from the chosen basis set while maintaining a rigorous and robust error control. This error control constitutes the main advantage over conceptually similar methods such as density fitting which rely on employing pre-defined auxiliary basis sets. We implemented the use of the CD in the framework of finite-field (ff) Hartree-Fock and ff second-order M{\o}ller Plesset perturbation theory. Our work demonstrates that the CD compression rates are particularly beneficial in calculations in the presence of a finite magnetic field. The ff-CD-MP2 scheme enables the correlated treatment of systems with more than 2000 basis functions in strong magnetic fields within a reasonable time span.