AI Article Synopsis
- The Meyer-Miller mapping model is a method used to study nonadiabatic dynamics and typically assumes the zero-point-energy (ZPE) parameter is positive.
- In reality, this ZPE parameter can be both negative and positive, with specific constraints needed for accuracy in modeling electronic states.
- The establishment of an exact mapping formulation allows the use of negative ZPE parameters to effectively describe dynamics in spin-boson models under certain conditions, performing well even at zero temperature.
Article 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 -electronic-state system actually requires γ∈(-1/, ∞) 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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| http://dx.doi.org/10.1021/acs.jpclett.1c00232 | DOI Listing |
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