Linear and angular momentum conservation in surface hopping methods

Yanze Wu; Jonathan Rawlinson; Robert G Littlejohn; Joseph E Subotnik

doi:10.1063/5.0179599

Linear and angular momentum conservation in surface hopping methods

J Chem Phys. 2024 Jan 14;160(2):024119. doi: 10.1063/5.0179599.

Authors

Yanze Wu¹, Jonathan Rawlinson², Robert G Littlejohn³, Joseph E Subotnik¹

Affiliations

¹ Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.
² Department of Mathematics, University of Manchester, Manchester M13 9PL, United Kingdom.
³ Department of Physics, University of California, Berkeley, California 94720, USA.

PMID: 38205852
DOI: 10.1063/5.0179599

Abstract

We demonstrate that, for systems with spin-orbit coupling and an odd number of electrons, the standard fewest switches surface hopping algorithm does not conserve the total linear or angular momentum. This lack of conservation arises not so much from the hopping direction (which is easily adjusted) but more generally from propagating adiabatic dynamics along surfaces that are not time reversible. We show that one solution to this problem is to run along eigenvalues of phase-space electronic Hamiltonians H(R, P) (i.e., electronic Hamiltonians that depend on both nuclear position and momentum) with an electronic-nuclear coupling Γ · P [see Eq. (25)], and we delineate the conditions that must be satisfied by the operator Γ. The present results should be extremely useful as far as developing new semiclassical approaches that can treat systems where the nuclear, electronic orbital, and electronic spin degrees of freedom altogether are all coupled together, hopefully including systems displaying the chiral-induced spin selectivity effect.