Paramagnetic NMR Shielding Tensors Based on Scalar Exact Two-Component and Spin-Orbit Perturbation Theory

Abstract

The temperature-dependent Fermi-contact and pseudocontact terms are important contributions to the paramagnetic NMR shielding tensor. Herein, we augment the scalar-relativistic (local) exact two-component (X2C) framework with spin-orbit perturbation theory including the screened nuclear spin-orbit correction for the EPR hyperfine coupling and g tensor to compute these temperature-dependent terms. The accuracy of this perturbative ansatz is assessed with the self-consistent spin-orbit two-component and four-component treatments serving as reference. This shows that the Fermi-contact and pseudocontact interaction is sufficiently described for paramagnetic NMR shifts, however, larger deviations are found for the EPR spectra and the principle components of the EPR properties of heavy elements. The impact of the perturbative treatment is further compared to that of the density functional approximation and the basis set. Large scale calculations are routinely possible with the multipole accelerated resolution of the identity approximation and the seminumerical exchange approximation as shown for [CeTi6O3(OiPr)9(salicylate)6].

Reducing Exact Two-Component Theory for NMR Couplings to a One-Component Approach: Efficiency and Accuracy

“…Overall, this one-component approach for the first-order terms is closely related to the one-component formulation of the hyperfine coupling constant in X2C. [90][91][92][93] Therefore, this anstatz can be easily implemented by interfacing the respective routines into a non-relativistic implementation of NMR coupling constants.…”