An extension of the fewest switches surface hopping algorithm to complex Hamiltonians and photophysics in magnetic fields: Berry's phase and "magnetic" forces

Abstract

We present a preliminary extension of the fewest switches surface hopping (FSSH) algorithm to the case of complex Hamiltonians as appropriate for modeling the dynamics of photoexcited molecules in magnetic fields. We make ansatze for the direction of momentum rescaling and we account for Berry's phase effects through "magnetic" forces as applicable in the adiabatic limit. Because Berry's phase is a nonlocal, topological characteristic of a set of entangled potential energy surfaces, we find that Tully's local FSSH algorithm can only partially capture the correct physics.

arXiv comment33 pages, 10 figures

References in corpus (4)

• Geometric phase effects in dynamics near conical intersections: Symmetry breaking and spatial localization
• Surface hopping from the perspective of quantum-classical Liouville dynamics
• When do we need to account for the geometric phase in excited state dynamics ?
• Why do mixed quantum-classical methods describe short-time dynamics through conical intersections so well? Analysis of geometric phase effects

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• A Phase-Space Semiclassical Approach for Modeling Nonadiabatic Nuclear Dynamics with Electronic Spin
• Calculating nonadiabatic couplings and Berry's phase by variational quantum eigensolvers
• Validating Fewest-Switches Surface Hopping in the Presence of Laser Fields
• A Reciprocal-Space Formulation of Surface Hopping
• Incorporating Berry Force Effects into The Fewest Switches Surface Hopping Algorithm: Intersystem Crossing and The Case of Electronic Degeneracy
• On the Proper Derivation of the Floquet-based Quantum Classical Liouville Equation and Surface Hopping Describing a Molecule or Material Subject to an External Field
• 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
• An Antisymmetric Berry Frictional Force At Equilibrium in the Presence of Spin-Orbit Coupling