6533b85bfe1ef96bd12bb5a0

RESEARCH PRODUCT

NMR chemical shift computations at second-order Møller-Plesset perturbation theory using gauge-including atomic orbitals and Cholesky-decomposed two-electron integrals.

Jürgen GaussSophia BurgerFilippo LippariniStella Stopkowicz

subject

Chemical Physics (physics.chem-ph)PhysicsChemical shiftMøller–Plesset perturbation theoryFOS: Physical sciencesGeneral Physics and AstronomyBasis functionElectronMagnetic fieldAtomic orbitalQuantum mechanicsPhysics::Atomic and Molecular ClustersPhysical and Theoretical ChemistryPerturbation theoryCholesky decomposition

description

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.

10.1063/5.0059633https://pubmed.ncbi.nlm.nih.gov/34418917