论文标题
非绝热动力学的Meyer-Miller映射模型中的负零点 - 能量参数
Negative Zero-Point-Energy Parameter in the Meyer-Miller Mapping Model for Nonadiabatic Dynamics
论文作者
论文摘要
著名的Meyer-Miller映射模型是生成基于实用轨迹的非绝热动态方法的有用方法。通常假定零点 - 能量（ZPE）参数为正。 F-电子状态系统的常规Meyer-Miller映射Hamiltonian中隐含的约束实际上要求每个电子自由度的ZPE参数大于-1/f的参数γis大于-1/f。对于这样的参数，负值都是可能的。我们首先建立一个严格的公式，以在应用约束时在笛卡尔相空间中构建精确的映射模型。当线性的半经典初始值表示近似核动力学时，负ZPE参数可能会导致相当良好的性能在描述典型的Spin-Boson模型中的动态行为，即使在挑战性零温度下，也可以用于凝结相阶段的两态系统。
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.
