Spin-orbit Hamiltonian for organic crystals from first principles electronic structure and Wannier functions

Abstract

Spin-orbit coupling in organic crystals is responsible for many spin-relaxation phenomena, going from spin diffusion to intersystem crossing. With the goal of constructing effective spin-orbit Hamiltonians to be used in multiscale approaches to the thermodynamical properties of organic crystals, we present a method that combines density functional theory with the construction of Wannier functions. In particular we show that the spin-orbit Hamiltonian constructed over maximally localised Wannier functions can be computed by direct evaluation of the spin-orbit matrix elements over the Wannier functions constructed in absence of spin-orbit interaction. This eliminates the prob- lem of computing the Wannier functions for almost degenerate bands, a problem always present with the spin-orbit-split bands of organic crystals. Examples of the method are presented for isolated molecules, for mono-dimensional chains of Pb and C atoms and for triarylamine-based one-dimansional single crystals.