Relativistic Kohn--Sham Theory of Paramagnetic Magnetic-Resonance Properties

Abstract

A general density functional theory based relativistic theory for paramagnetic NMR (pNMR) shifts, EPR g-tensors and hyperfine coupling tensors as well as magnetizabilities is derived. The formulation uses spin--orbit exact two-component (X2C) theory, gauge-including atomic orbitals, and generalized complex Kohn--Sham response equations with all ingredients being implemented analytically with the help of Goldstone modes and an orientation-constrained shielding. Additionally, we describe a two-component augmented Roothaan--Hall (ARH) solver for robust and stable convergence, which ensures that both a stationary point and a minimum are found. This is crucial for the convergence of the response equations for properties of paramagnetic systems. The extension of common population analyses for the two-component theory to aid in the interpretation of the spectra is further described. Using these new techniques, we are able to analyze the success and failure of density functional theory for relativistic open-shell systems including actinide complexes.