NMR Chemical Shift Computations at Second-Order Møller-Plesset Perturbation Theory Using Gauge-Including Atomic Orbitals and Cholesky-Decomposed Two-Electron Integrals

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.

12 pages, 2 figures

Cited by in corpus (4)

• Cholesky decomposition of complex two-electron integrals over GIAOs: Efficient MP2 computations for large molecules in strong magnetic fields
• A black-box, general purpose quadratic self-consistent field code with and without Cholesky Decomposition of the two-electron integrals
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• Computation of NMR shieldings at the CASSCF level using gauge-including atomic orbitals and Cholesky decomposition