Liu Zengkui, Lyu Ningyi, Hu Zhubin, Zeng Hao, Batista Victor S, Sun Xiang
Division of Arts and Sciences, NYU Shanghai, 567 West Yangsi Road, Shanghai 200124, China.
NYU-ECNU Center for Computational Chemistry at NYU Shanghai, 3663 Zhongshan Road North, Shanghai 200062, China.
J Chem Phys. 2024 Jul 14;161(2). doi: 10.1063/5.0208708.
Accurate quantum dynamics simulations of nonadiabatic processes are important for studies of electron transfer, energy transfer, and photochemical reactions in complex systems. In this comparative study, we benchmark various approximate nonadiabatic dynamics methods with mapping variables against numerically exact calculations based on the tensor-train (TT) representation of high-dimensional arrays, including TT-KSL for zero-temperature dynamics and TT-thermofield dynamics for finite-temperature dynamics. The approximate nonadiabatic dynamics methods investigated include mixed quantum-classical Ehrenfest mean-field and fewest-switches surface hopping, linearized semiclassical mapping dynamics, symmetrized quasiclassical dynamics, the spin-mapping method, and extended classical mapping models. Different model systems were evaluated, including the spin-boson model for nonadiabatic dynamics in the condensed phase, the linear vibronic coupling model for electronic transition through conical intersections, the photoisomerization model of retinal, and Tully's one-dimensional scattering models. Our calculations show that the optimal choice of approximate dynamical method is system-specific, and the accuracy is sensitively dependent on the zero-point-energy parameter and the initial sampling strategy for the mapping variables.
对非绝热过程进行精确的量子动力学模拟，对于研究复杂系统中的电子转移、能量转移和光化学反应非常重要。在这项比较研究中，我们使用映射变量对各种近似非绝热动力学方法与基于高维数组的张量列车（TT）表示的数值精确计算进行基准测试，包括用于零温动力学的TT-KSL和用于有限温动力学的TT-热场动力学。所研究的近似非绝热动力学方法包括混合量子-经典埃伦费斯特平均场和最少跃迁表面跳跃、线性化半经典映射动力学、对称化准经典动力学、自旋映射方法以及扩展经典映射模型。评估了不同的模型系统，包括凝聚相中用于非绝热动力学的自旋-玻色子模型、通过锥形交叉点进行电子跃迁的线性振子耦合模型、视黄醛的光异构化模型以及塔利的一维散射模型。我们的计算表明，近似动力学方法的最佳选择是依赖于系统的，并且精度敏感地取决于零点能量参数和映射变量的初始采样策略。
