Treating geometric phase effects in nonadiabatic dynamics

TL;DR

This paper introduces a method to eliminate gauge ambiguity in nonadiabatic dynamics with geometric phase effects, enabling gauge-invariant derivative couplings for more accurate simulations.

Contribution

It proposes a bottom-up construction of a parametric quantum Hamiltonian to identify gauge-invariant derivative couplings in systems with geometric phase effects.

Findings

Successfully applied to surface hopping calculations across an avoided crossing.

Achieved fully gauge-invariant derivative couplings in tested scenarios.

Demonstrated potential for improved nonadiabatic dynamics simulations.

Abstract

We present an approach for eliminating the gauge freedom for derivative couplings in nonadiabatic dynamics in the presence of geometric phase effects. This approach relies on a bottom-up construction of a parametric quantum Hamiltonian in terms of functions of a dynamical variable, which can be associated with real and imaginary-valued contributions to the Hamiltonian in a given diabatic basis. By minimizing the deviation of the imaginary functions from a constant we identify a set of diabatic bases that recover the real-valued gauge commonly used for topologically-trivial systems. This minimization, however, also confines the gauge freedom in the topologically-nontrivial case, opening a path towards finding gauge-invariant derivative couplings under geometric phase effects. Encouraging results are presented for fewest-switches surface hopping calculations of a nuclear wavepacket traversing a single avoided crossing, for which fully gauge-invariant derivative couplings are found.