在基于轨迹的非绝热动力学中不计成本地明确纳入光激发

Jiří Janoš, Petr Slavíček, Basile F. E. Curchod
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引用次数: 0

摘要

在过去的几十年里,理论光化学产生了多种模拟分子非绝热动力学的技术。令人惊讶的是,人们在充分描述光化学或光物理过程的第一步--光激发--方面所做的努力要少得多。在此,我们提出了一种形式主义,在基于轨迹的非绝热动力学中,将激光脉冲的效应包含在初始条件的水平上,而不增加额外的成本。提升密度方法(PDA)通过定义一组新的初始条件(包括激发时间),将激发与非绝热动力学分离开来。带有表面跳变的 PDA 使非绝热动力学模拟与使用显式激光脉冲的量子动力学模拟非常一致,并突出了激光脉冲对所产生的光动力学和(突然)垂直激发极限的强烈影响。利用本研究提供的代码,可以将 PDA 与基于轨迹的非绝热方法结合起来,用于任意大小的分子。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Including photoexcitation explicitly in trajectory-based nonadiabatic dynamics at no cost
Over the last decades, theoretical photochemistry has produced multiple techniques to simulate the nonadiabatic dynamics of molecules. Surprisingly, much less effort has been devoted to adequately describing the first step of a photochemical or photophysical process: photoexcitation. Here, we propose a formalism to include the effect of a laser pulse in trajectory-based nonadiabatic dynamics at the level of the initial conditions, with no additional cost. The promoted density approach (PDA) decouples the excitation from the nonadiabatic dynamics by defining a new set of initial conditions, which include an excitation time. PDA with surface hopping leads to nonadiabatic dynamics simulations in excellent agreement with quantum dynamics using an explicit laser pulse and highlights the strong impact of a laser pulse on the resulting photodynamics and the limits of the (sudden) vertical excitation. Combining PDA with trajectory-based nonadiabatic methods is possible for any arbitrary-sized molecules using a code provided in this work.
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