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A multi-state trajectory method for non-adiabatic dynamics simulations

机译:非绝热动力学模拟的多态轨迹方法

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A multi-state trajectory approach is proposed to describe nuclear-electron coupled dynamics in nonadiabatic simulations. In this approach, each electronic state is associated with an individual trajectory, among which electronic transition occurs. The set of these individual trajectories constitutes a multi-state trajectory, and nuclear dynamics is described by one of these individual trajectories as the system is on the corresponding state. The total nuclear-electron coupled dynamics is obtained from the ensemble average of the multi-state trajectories. A variety of benchmark systems such as the spin-boson system have been tested and the results generated using the quasi-classical version of the method show reasonably good agreement with the exact quantum calculations. Featured in a clear multi-state picture, high efficiency, and excellent numerical stability, the proposed method may have advantages in being implemented to realistic complex molecular systems, and it could be straightforwardly applied to general nonadiabatic dynamics involving multiple states. (C) 2016 Author(s).
机译:提出了一种多态轨迹方法来描述非绝热模拟中的核电子耦合动力学。在这种方法中,每个电子状态都与一个单独的轨迹相关联,其中发生了电子跃迁。这些单个轨迹的集合构成了多状态轨迹,并且当系统处于相应状态时,核动力学由这些单个轨迹之一来描述。总的核电子耦合动力学是从多态轨迹的集合平均获得的。已经测试了各种基准系统,例如自旋玻色子系统,并且使用该方法的准经典版本生成的结果与精确的量子计算显示出相当好的一致性。该方法具有清晰的多态图谱,高效率和出色的数值稳定性等特点,在现实的复杂分子系统中可能具有优势,可以直接应用于涉及多态的一般非绝热动力学。 (C)2016作者。

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