Incorporating Berry Force Effects into The Fewest Switches Surface Hopping Algorithm: Intersystem Crossing and The Case of Electronic Degeneracy

Abstract

We present a preliminary surface-hopping approach for modeling intersystem crossing (ISC) dynamics between four electronic states: one singlet and one (triply degenerate) triplet. In order to incorporate all Berry force effects, the algorithm requires that, when moving along an adiabatic surface associated with the triplet manifold, \mycomment{one must also keep track of a quasi-diabatic index (akin to a "$m_s$" quantum number) for each trajectory. For a simple model problem, we find that a great deal of new physics can be captured by our algorithm, setting the stage for larger, more realistic (or perhaps even {\em ab initio}) simulations in the future.

References in corpus (2)

• Chemical Reaction Rates for Systems with Spin-Orbit Coupling and an Odd Number of Electrons: Does Berry's Phase Lead to Meaningful Spin-Dependent Nuclear Dynamics for a Two State Crossing?
• An extension of the fewest switches surface hopping algorithm to complex Hamiltonians and photophysics in magnetic fields: Berry's phase and "magnetic" forces

Cited by in corpus (5)

• Modeling Spin-Dependent Nonadiabatic Dynamics with Electronic Degeneracy: A Phase-Space Surface-Hopping Method
• A Phase-Space Semiclassical Approach for Modeling Nonadiabatic Nuclear Dynamics with Electronic Spin
• On the Meaning of Berry Force For Unrestricted Systems Treated With Mean-Field Electronic Structure
• 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