Modeling Spin-Dependent Nonadiabatic Dynamics with Electronic Degeneracy: A Phase-Space Surface-Hopping Method

Abstract

Nuclear Berry curvature effects emerge from electronic spin degeneracy and canlead to non-trivial spin-dependent (nonadiabatic) nuclear dynamics. However, such effects are completely neglected in all current mixed quantum-classical methods such as fewest switches surface-hopping. In this work, we present a phase-space surface-hopping (PSSH) approach to simulate singlet-triplet intersystem crossing dynamics. We show that with a simple pseudo-diabatic ansatz, a PSSH algorithm can capture the relevant Berry curvature effects and make predictions in agreement with exact quantum dynamics for a simple singlet-triplet model Hamiltonian. Thus, this approach represents an important step towards simulating photochemical and spin processes concomitantly, as relevant to intersystem crossing and spin-lattice relaxation dynamics.

References in corpus (8)

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Cited by in corpus (4)

• Total Angular Momentum Conservation in Ab Initio Born-Oppenheimer Molecular Dynamics
• The Effect of Duschinskii Rotations on Spin-Dependent Electron Transfer Dynamics
• A Quantum-Classical Liouville Formalism in a Preconditioned Basis and Its Connection with Phase-Space Surface Hopping
• Spin-Dependent Stereochemistry: A Non-adiabatic Quantum Dynamics Case Study of S + H2 -> SH + H Reaction