Nonadiabatic transition paths from quantum jump trajectories.
Nonadiabatic transition paths from quantum jump trajectories.
复制标题
量子跳跃轨迹的非绝热跃迁路径。
DOI：
10.1063/5.0102891
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
David T. Limmer
中科院分区：
文献类型：
--
作者：
Michelle C Anderson;A. Schile;David T. Limmer
本文提出了一种利用跃迁路径理论和量子跃迁轨迹系综研究开放量子系统中稀有反应路径的方法。当系统嵌入在马尔可夫环境中时，这种方法允许阐明耗散的非绝热动力学的反应路径。我们详细介绍了热激活过程的主要途径和速率，以及在圆锥交叉的最小模型中垂直激发后的弛豫途径和光产率。通过对热障穿越事件的committor函数的推广，我们发现圆锥相交的几何形状影响过渡态的电子特性。同样，几何结构改变了垂直激发后的弛豫机制。小的非绝热耦合引起的模型弛豫通过纯减相主导的途径进行，而大的非绝热耦合引起的模型弛豫通过耗散限制的途径进行。这里介绍的开放量子系统的非绝热动力学的观点将经典的反应路径概念推广到基本的量子力学过程。
We present a means of studying rare reactive pathways in open quantum systems using transition path theory and ensembles of quantum jump trajectories. This approach allows for the elucidation of reactive paths for dissipative, nonadiabatic dynamics when the system is embedded in a Markovian environment. We detail the dominant pathways and rates of thermally activated processes and the relaxation pathways and photoyields following vertical excitation in a minimal model of a conical intersection. We find that the geometry of the conical intersection affects the electronic character of the transition state as defined through a generalization of a committor function for a thermal barrier crossing event. Similarly, the geometry changes the mechanism of relaxation following a vertical excitation. Relaxation in models resulting from small diabatic coupling proceeds through pathways dominated by pure dephasing, while those with large diabatic coupling proceed through pathways limited by dissipation. The perspective introduced here for the nonadiabatic dynamics of open quantum systems generalizes classical notions of reactive paths to fundamentally quantum mechanical processes.
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影响因子：
3.3
作者：
Zheng, Weihua;Gallicchio, Emilio;Deng, Nanjie;Andrec, Michael;Levy, Ronald M.
通讯作者：
Levy, Ronald M.
影响因子：
4.4
作者：
Hele, Timothy J. H.;Willatt, Michael J.;Althorpe, Stuart C.
通讯作者：
Althorpe, Stuart C.
DOI：
10.1021/acs.jpca.9b00877
发表时间：
2019-02
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
Xuecheng Tao;Philip Shushkov;Thomas F. Miller
通讯作者：
Xuecheng Tao;Philip Shushkov;Thomas F. Miller
影响因子：
1.6
作者：
Carollo, Federico;Garrahan, Juan P.;Jack, Robert L.
通讯作者：
Jack, Robert L.
影响因子：
15
作者：
Yu TQ;Lapelosa M;Vanden-Eijnden E;Abrams CF
通讯作者：
Abrams CF