Department of Physics, Rutgers University, Newark, New Jersey 07102, United States.
Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, United States.
J Phys Chem Lett. 2022 Feb 24;13(7):1785-1790. doi: 10.1021/acs.jpclett.1c04132. Epub 2022 Feb 16.
A surface-hopping algorithm recently derived from the exact factorization approach, SHXF [Ha et al. , , 1097], introduces an additional term in the electronic equation of surface hopping that couples electronic states through the quantum momentum. This term not only provides a first-principles description of decoherence, but here we show it is crucial to accurately capture nonadiabatic dynamics when more than two states are occupied at any given time. Using a vibronic coupling model of the uracil cation, we show that the lack of this term in traditional surface-hopping methods, including those with decoherence corrections, leads to failure to predict the dynamics through a three-state intersection, while SHXF performs similarly to the multiconfiguration time-dependent Hartree quantum dynamics benchmark.
一种最近从精确因式分解方法导出的表面跳跃算法，即 SHXF [Ha 等人，，1097]，在电子方程中引入了一个附加项，该附加项通过量子动量来耦合电子态。该项不仅为退相干提供了一个第一性原理的描述，但在这里我们表明，当在任何给定时间有超过两个状态被占据时，它对于准确捕捉非绝热动力学是至关重要的。我们使用尿嘧啶阳离子的振子耦合模型表明，在传统的表面跳跃方法中缺乏这个项，包括那些具有退相干修正的方法，导致它们无法预测通过三态交叉的动力学，而 SHXF 的表现与多组态含时哈特ree 量子动力学基准相似。
