Thermal equilibrium properties of surface hopping with an implicit Langevin bath.
Thermal equilibrium properties of surface hopping with an implicit Langevin bath.
复制标题
使用隐式朗之万浴的表面跳跃的热平衡特性。
DOI：
10.1063/1.4905253
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
S. Corcelli
中科院分区：
文献类型：
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作者：
M. C. Sherman;S. Corcelli
在一个三位电子转移模型的背景下，对最少开关表面跃迁(FSSH)方法建立和维持适当热平衡的能力进行了评估。电子转移模型由三个耦合的非绝热状态组成，每个非绝热状态都与集合浴坐标相协调。这导致了绝热表象中能量增加的三个态。在宽的温度范围和三种不同的非绝热耦合强度下，监测了250 ns FSSH-L模拟过程中的绝热布居和集体溶剂坐标的分布。绝热布居比和溶剂坐标分布的数值模拟结果与FSSH-L模拟结果吻合较好。FSSH-L方法得到了正确的玻尔兹曼分布，但积分布居略有错误，因为FSSH不严格遵守详细平衡。在高温和高非绝热耦合情况下，总体上符合得更好，这与先前报道的分析和模拟分析相一致[J.R.Schmidt，P.V.Parandekar和J.C.Tully，J.Chem。太棒了。129,044104(2008年)]一个耦合到古典浴缸的两级系统。
The ability of fewest switches surface hopping (FSSH) approach, where the classical degrees of freedom are coupled to an implicit Langevin bath, to establish and maintain an appropriate thermal equilibrium was evaluated in the context of a three site model for electron transfer. The electron transfer model consisted of three coupled diabatic states that each depends harmonically on the collective bath coordinate. This results in three states with increasing energy in the adiabatic representation. The adiabatic populations and distributions of the collective solvent coordinate were monitored during the course of 250 ns FSSH-Langevin (FSSH-L) simulations performed at a broad range of temperatures and for three different nonadiabatic coupling strengths. The agreement between the FSSH-L simulations and numerically exact results for the adiabatic population ratios and solvent coordinate distributions was generally favorable. The FSSH-L method produces a correct Boltzmann distribution of the solvent coordinate on each of the adiabats, but the integrated populations are slightly incorrect because FSSH does not rigorously obey detailed balance. The overall agreement is better at high temperatures and for high nonadiabatic coupling, which agrees with a previously reported analytical and simulation analysis [J. R. Schmidt, P. V. Parandekar, and J. C. Tully, J. Chem. Phys. 129, 044104 (2008)] on a two-level system coupled to a classical bath.