论文标题
用于非绝热动力学的部分线性化旋转映射方法。 I.理论的推导
A partially linearized spin-mapping approach for nonadiabatic dynamics. I. Derivation of the theory
论文作者
论文摘要
我们提出了一种新的基于部分线性映射的方法，用于近似于凝结相的非绝热系统中的实时量子相关函数，称为spin-pldm。在经典的轨迹图片中，部分线性化的方法通过明确进化两组映射变量来分别处理向前和向后路径的电子动力学。与先前基于Meyer-Miller-Stock-Thoss映射的先前派生的部分线性化方法不同，Spin-Pldm使用Stratonovich-Weyl变换来描述自旋图空间内每个路径的电子动力学；这会自动限制笛卡尔映射变量位于超级球上，这意味着经典运动方程将不再能够从物理子空间中传播映射变量。严格衍生的零点能量参数的存在也将Spin-PLDM与其他部分线性化方法区分开。与同一类中的其他方法相比，这些新功能似乎给出了计算动态观察值的方法的卓越精度。在本文中，通过将方法应用于多种自旋玻色子模型以及Fenna-Matthews-Olsen复合物，可以在本文中证明Spin-PLDM的出色精度。
We present a new partially linearized mapping-based approach for approximating real-time quantum correlation functions in condensed-phase nonadiabatic systems, called spin-PLDM. Within a classical trajectory picture, partially linearized methods treat the electronic dynamics along forward and backward paths separately by explicitly evolving two sets of mapping variables. Unlike previously derived partially linearized methods based on the Meyer-Miller-Stock-Thoss mapping, spin-PLDM uses the Stratonovich-Weyl transform to describe the electronic dynamics for each path within the spin-mapping space; this automatically restricts the Cartesian mapping variables to lie on a hypersphere and means that the classical equations of motion can no longer propagate the mapping variables out of the physical subspace. The presence of a rigorously derived zero-point energy parameter also distinguishes spin-PLDM from other partially linearized approaches. These new features appear to give the method superior accuracy for computing dynamical observables of interest, when compared with other methods within the same class. The superior accuracy of spin-PLDM is demonstrated within this paper through application of the method to a wide range of spin-boson models, as well as to the Fenna-Matthews-Olsen complex.
