Path integral molecular dynamics with surface hopping for thermal equilibrium sampling of nonadiabatic systems

Abstract

In this work, a novel ring polymer representation for multi-level quantum system is proposed for thermal average calculations. The proposed presentation keeps the discreteness of the electronic states: besides position and momentum, each bead in the ring polymer is also characterized by a surface index indicating the electronic energy surface. A path integral molecular dynamics with surface hopping (PIMD-SH) dynamics is also developed to sample the equilibrium distribution of ring polymer configurational space. The PIMD-SH sampling method is validated theoretically and by numerical examples.

References in corpus (13)

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Cited by in corpus (14)

• Coherent State Mapping Ring-Polymer Molecular Dynamics for Non-Adiabatic quantum propagations
• State Dependent Ring Polymer Molecular Dynamics for Investigating Excited Nonadiabatic Dynamics
• Path Integral Molecular Dynamics for Exact Quantum Statistics of Multi-Electronic-State Systems
• An analysis of isomorphic RPMD in the golden rule limit
• Nonadiabatic quantum transition-state theory in the golden-rule limit. I. Theory and application to model systems
• Quasi-classical approaches to vibronic spectra revisited
• Nonadiabatic quantum transition-state theory in the golden-rule limit. II. Overcoming the pitfalls of the saddle-point and semiclassical approximations
• A Reciprocal-Space Formulation of Surface Hopping
• Simulating vibronic spectra via Matsubara dynamics: coping with the sign problem
• Accelerated sampling by infinite swapping of path integral molecular dynamics with surface hopping
• Data clustering based on Langevin annealing with a self-consistent potential
• Continuum limit and preconditioned Langevin sampling of the path integral molecular dynamics
• The Bayesian Inversion Problem for Thermal Average Sampling of Quantum Systems
• Multi-level Monte Carlo path integral molecular dynamics for thermal average calculation in the nonadiabatic regime