Efficient Treatment of Relativistic Effects with Periodic Density Functional Methods: Energies, Gradients, and Stress Tensors

Abstract

The implementation of an efficient self-consistent field (SCF) method including both scalar relativistic effects and spin-orbit interaction in density functional theory (DFT) is presented. We make use of Gaussian-type orbitals (GTOs) and all integrals are evaluated in real space. Our implementation supports density functional approximations up to the level of meta-generalized gradient approximations (mGGAs) for SCF energies and gradients. The latter can be used to compute the stress tensor and consequently allow us to optimize the cell structure. Considering spin-orbit interaction requires the extension of the standard procedures to a two-component (2c) formalism and a non-collinear approach for open-shell systems. Here, we implemented both the canonical and the Scalmani-Frisch non-collinear DFT formalisms, with hybrid and range-separated hybrid functionals being presently restricted to SCF energies. We demonstrate both efficiency and relevance of spin-orbit effects for the electronic structure of discrete systems and systems periodic in one to three dimensions.

main text (24 pages, 3 figures) and supplemental material (51 pages, 4 figures)

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• Current density functional framework for spin-orbit coupling: Extension to periodic systems