NMR Chemical Shift Computations at Second-Order M{\o}ller-Plesset Perturbation Theory Using Gauge-Including Atomic Orbitals and Cholesky-Decomposed Two-Electron Integrals

TL;DR

This paper presents a novel computational scheme combining gauge-including atomic orbitals and Cholesky decomposition to efficiently and accurately compute NMR shieldings at the second-order Møller-Plesset perturbation theory level, enabling large-scale molecular calculations.

Contribution

The authors develop and implement a GIAO-MP2 scheme with Cholesky decomposition for NMR shielding calculations, improving efficiency and scalability over previous methods.

Findings

Cholesky decomposition accurately approximates two-electron integral derivatives.

The scheme achieves reliable NMR shielding results for molecules with over 100 atoms.

The method is applicable to large basis sets with over 1000 functions.

Abstract

We report on a formulation and implementation of a scheme to compute NMR shieldings at second-order Moller-Plesset (MP2) perturbation theory using gauge-including atomic orbitals (GIAOs) to ensure gauge-origin independence and Cholesky decomposition (CD) to handle unperturbed as well as perturbed two-electron integrals. We investigate the accuracy of the CD for the derivatives of the two-electron integrals with respect to an external magnetic field as well as for the computed NMR shieldings, before we illustrate the applicability of our CD based GIAO-MP2 scheme in calculations involving up to about one hundred atoms and more than one thousand basis functions.