Surface hopping methodology in laser-driven molecular dynamics

Abstract

A theoretical justification of the empirical surface hopping method for the laser-driven molecular dynamics is given utilizing the formalism of the exact factorization of the molecular wavefunction [Abedi et al., PRL $\text{105}$, 123002 (2010)] in its quantum-classical limit. Employing an exactly solvable ${\text{H}}_2^{+}$-like model system, it is shown that the deterministic classical nuclear motion on a single time-dependent surface in this approach describes the same physics as stochastic (hopping-induced) motion on several surfaces, provided Floquet surfaces are applied. Both quantum-classical methods do describe reasonably well the exact nuclear wavepacket dynamics for extremely different dissociation scenarios. Hopping schemes using Born-Oppenheimer surfaces or instantaneous Born-Oppenheimer surfaces fail completely.

References in corpus (5)

• Exact factorization of the time-dependent electron-nuclear wavefunction
• Correlated electron-nuclear dynamics: Exact factorization of the molecular wavefunction
• A coupled-trajectory quantum-classical approach to decoherence in non-adiabatic processes
• Is the molecular Berry phase an artifact of the Born-Oppenheimer approximation?
• Surface hopping from the perspective of quantum-classical Liouville dynamics

Cited by in corpus (10)

• Light-Matter Interactions via the Exact Factorization Approach
• Exact Potential Energy Surface for Molecules in Cavities
• Ultrafast dynamics with the exact factorization
• On the Numerical Solution of the Exact Factorization Equations
• Roadmap for Molecular Benchmarks in Nonadiabatic Dynamics
• Quantum-classical nonadiabatic dynamics of Floquet driven systems
• Validating Fewest-Switches Surface Hopping in the Presence of Laser Fields
• 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
• Predictive Semiclassical Model for Coherent and Incoherent Emission in the Strong Field Regime: The Mollow Triplet Revisited
• Unraveling Abnormal Collective Effects via the Non-Monotonic Number Dependence of Electron Transfer in Confined Electromagnetic Fields