On the meaning of Berry force for unrestricted systems treated with mean-field electronic structure

摘要

We show that the Berry force as computed by an approximate, mean-field electronic structure can be meaningful if properly interpreted. In particular, for a model Hamiltonian representing a molecular system with an even number of electrons interacting via a two-body (Hubbard) interaction and a spin-orbit coupling, we show that a meaningful nonzero Berry force emerges whenever there is spin unrestriction-even though the Hamiltonian is real-valued and formally the on-diagonal single-surface Berry force must be zero. Moreover, if properly applied, this mean-field Berry force yields roughly the correct asymptotic motion for scattering through an avoided crossing. That being said, within the context of a ground-state calculation, several nuances do arise as far interpreting the Berry force correctly, and as a practical matter, the Berry force diverges near the Coulson-Fischer point (which can lead to numerical instabilities). We do not address magnetic fields here. Published under an exclusive license by AIP Publishing.