Negative Zero-Point-Energy Parameter in the Meyer-Miller Mapping Model for Nonadiabatic Dynamics

Abstract

The celebrated Meyer-Miller mapping model has been a useful approach for generating practical trajectory-based nonadiabatic dynamics methods. It is generally assumed that the zero-point-energy (ZPE) parameter is positive. The constraint implied in the conventional Meyer-Miller mapping Hamiltonian for an F-electronic-state system actually requires that parameter γis larger than -1/F for the ZPE parameter for each electronic degree of freedom. Both negative and positive values are possible for such a parameter. We first establish a rigorous formulation to construct exact mapping models in the Cartesian phase space when the constraint is applied. When nuclear dynamics is approximated by the linearized semiclassical initial value representation, a negative ZPE parameter could lead to reasonably good performance in describing dynamic behaviors in typical spin-boson models for condensed-phase two-state systems, even at challenging zero temperature.

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• Non-Adiabatic Ring Polymer Molecular Dynamics with Spin Mapping Variables
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• Twin-Space Representation of Classical Mapping Model in the Constraint Phase Space Representation: Numerically Exact Approach to Open Quantum Systems
• Electron transfer at electrode interfaces via a straightforward quasiclassical fermionic mapping approach
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• NQCDynamics.jl: A Julia Package for Nonadiabatic Quantum Classical Molecular Dynamics in the Condensed Phase