Application of the noncollinear Scalmani–Frisch formalism to current density functional theory

Abstract

We generalize the noncollinear formalism proposed by Scalmani and Frisch [J. Chem. Theory Comput. 8, 2193 (2012)] to include the particle and spin current densities for meta-generalized gradient approximations and local hybrid functionals. This allows us to fully include the impact of spin–orbit coupling in relativistic calculations and for applications to finite magnetic fields. For the latter, we use London atomic orbitals to ensure gauge origin invariance. It is shown that this formalism is superior to the more common canonical noncollinear approach in relativistic calculations, as it naturally includes all three spin current densities in the closed-shell limit and avoids the projection onto the spin magnetization vector. This is important to easily restore rotational invariance in this limit. In addition, the Scalmani–Frisch approach can be made numerically stable and may lead to a nonvanishing local magnetic torque. However, both formalisms are rotationally invariant for open-shell systems and in finite magnetic fields.