An efficient solution to the decoherence enhanced trivial crossing problem in surface hopping
An efficient solution to the decoherence enhanced trivial crossing problem in surface hopping
复制标题
表面跳跃中退相干增强的琐碎交叉问题的有效解决方案
DOI：
10.1063/1.5020693
复制
发表时间：
2018-03-14
影响因子：
4.4
通讯作者：
Wang, Linjun
中科院分区：
文献类型：
--
作者：
Bai, Xin;Qiu, Jing;Wang, Linjun
我们对Tully的最少开关表面跳跃(FSSH)算法同时应用平凡交叉和退相干校正时的时间间隔收敛进行了深入研究。以一种基于力的消相干策略和一种基于能量的消相干策略为例，我们证明了消相干校正本质上增强了平凡的交叉问题。我们提出了一种受限退相干(RD)策略，并将其引入到自洽(SC)最少开关表面跳跃算法[L.Wang和O.V.Prezhdo，J.Phys.化学。让我们来吧。5713(2014)]。所得到的SC-FSSH-RD方法被应用于具有不同电子耦合和电子-声子耦合的一般哈密顿量，以模拟数十到数百个分子中的电荷输运。在所有情况下，SC-FSSH-RD允许我们使用0.1ms的大时间间隔进行收敛，并且仿真时间减少了一个数量级以上。我们完美地捕捉到了电荷输运的带机制和跳跃机制。SC-FSSH-RD在绝热表象中进行表面跳跃，并可在波函数传播的非绝热表象和局部非绝热表象中实现。SC-FSSH-RD可以潜在地描述有机物和其他材料中电子和激子的一般非绝热动力学。由AIP出版公司出版。
We provide an in-depth investigation of the time interval convergence when both trivial crossing and decoherence corrections are applied to Tully's fewest switches surface hopping (FSSH) algorithm. Using one force-based and one energy-based decoherence strategies as examples, we show decoherence corrections intrinsically enhance the trivial crossing problem. We propose a restricted decoherence (RD) strategy and incorporate it into the self-consistent (SC) fewest switches surface hopping algorithm [L. Wang and O. V. Prezhdo, J. Phys. Chem. Lett. 5, 713 (2014)]. The resulting SC-FSSH-RD approach is applied to general Hamiltonians with different electronic couplings and electron-phonon couplings to mimic charge transport in tens to hundreds of molecules. In all cases, SC-FSSH-RD allows us to use a large time interval of 0.1 fs for convergence and the simulation time is reduced by over one order of magnitude. Both the band and hopping mechanisms of charge transport have been captured perfectly. SC-FSSH-RD makes surface hops in the adiabatic representation and can be implemented in both diabatic and locally diabatic representations for wave function propagation. SC-FSSH-RD can potentially describe general nonadiabatic dynamics of electrons and excitons in organics and other materials. Published by AIP Publishing.