Negative zero-point-energy parameter in the Meyer-Miller mapping model for nonadiabatic dynamics

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 γ∈(−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.

Recommended citation: He, X.; Gong, Z.; Wu, B.; Liu, J. Negative Zero-Point-Energy Parameter in the Meyer-Miller Mapping Model for Nonadiabatic Dynamics. The Journal of Physical Chemistry Letters 2021, 12 (10), 2496–2501. https://doi.org/10.1021/acs.jpclett.1c00232.
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