Mannouch Jonathan R, Richardson Jeremy O
Laboratory of Physical Chemistry, ETH Zürich, 8093 Zürich, Switzerland.
J Chem Phys. 2020 Nov 21;153(19):194109. doi: 10.1063/5.0031168.
We present a new partially linearized mapping-based approach for approximating real-time quantum correlation functions in condensed-phase nonadiabatic systems, called the spin partially linearized density matrix (spin-PLDM) approach. 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 in this paper through application of the method to a wide range of spin-boson models as well as to the Fenna-Matthews-Olsen complex.
我们提出了一种新的基于部分线性化映射的方法，用于近似凝聚相非绝热系统中的实时量子关联函数，称为自旋部分线性化密度矩阵（spin-PLDM）方法。在经典轨迹图景中，部分线性化方法通过明确演化两组映射变量，分别处理沿正向和反向路径的电子动力学。与先前基于迈耶 - 米勒 - 斯托克 - 托斯映射推导的部分线性化方法不同，spin-PLDM使用斯特拉托诺维奇 - 外尔变换来描述自旋映射空间内每条路径的电子动力学；这自动将笛卡尔映射变量限制在超球面上，意味着经典运动方程不再能将映射变量传播出物理子空间。严格推导的零点能量参数的存在也使spin-PLDM与其他部分线性化方法区分开来。与同一类中的其他方法相比，这些新特性似乎使该方法在计算感兴趣的动力学可观测量时具有更高的精度。本文通过将该方法应用于广泛的自旋 - 玻色子模型以及费纳 - 马修斯 - 奥尔森复合体，证明了spin-PLDM的卓越精度。
