Nonadiabatic Dynamics in a Laser Field: Using Floquet Fewest Switches Surface Hopping To Calculate Electronic Populations for Slow Nuclear Velocities.,Journal of Chemical Theory and Computation

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Nonadiabatic Dynamics in a Laser Field: Using Floquet Fewest Switches Surface Hopping To Calculate Electronic Populations for Slow Nuclear Velocities.
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2020-01-17 , DOI: 10.1021/acs.jctc.9b00950
Zeyu Zhou ₁ , Hsing-Ta Chen ₁ , Abraham Nitzan ₁ , Joseph Eli Subotnik ₁

Affiliation

We investigate two well-known approaches for extending the fewest switches surface hopping (FSSH) algorithm to periodic time-dependent couplings. The first formalism acts as if the instantaneous adiabatic electronic states were standard adiabatic states, which just happen to evolve in time. The second formalism replaces the role of the usual adiabatic states by the time-independent adiabatic Floquet states. For a set of modified Tully model problems, the Floquet FSSH (F-FSSH) formalism gives a better estimate for both transmission and reflection probabilities than the instantaneous adiabatic FSSH (IA-FSSH) formalism, especially for slow nuclear velocities. More importantly, only F-FSSH predicts the correct final scattering momentum. Finally, in order to use Floquet theory accurately, we find that it is crucial to account for the interference between wavepackets on different Floquet states. Our results should be of interest to all those interested in laser-induced molecular dynamics.

中文翻译：

激光场中的非绝热动力学：使用Floquet Fewest开关表面跳变来计算核速慢的电子种群。

我们研究了两种众所周知的方法，可将最少的开关表面跳变（FSSH）算法扩展到与时间有关的周期性耦合。第一种形式主义的行为就好像瞬时绝热电子状态是标准绝热状态一样，它们恰好随时间变化。第二种形式主义用与时间无关的绝热浮球状态代替了通常的绝热状态。对于一组修改后的塔利模型问题，与瞬时绝热FSSH（IA-FSSH）形式主义相比，Floquet FSSH（F-FSSH）形式主义对透射和反射概率都提供了更好的估计，尤其是对于核速度较慢的情况。更重要的是，只有F-FSSH可以预测正确的最终散射动量。最后，为了准确地使用Floquet理论，我们发现解决不同Floquet状态下的波包之间的干扰至关重要。所有对激光诱导的分子动力学感兴趣的人都应该对我们的结果感兴趣。

更新日期：2020-01-21

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