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 phasespace 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 chiralinduced spin selectivity effect.
 Award ID(s):
 2102402
 NSFPAR ID:
 10418740
 Date Published:
 Journal Name:
 The Journal of Chemical Physics
 Volume:
 157
 Issue:
 1
 ISSN:
 00219606
 Page Range / eLocation ID:
 011101
 Format(s):
 Medium: X
 Sponsoring Org:
 National Science Foundation
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