Martinez Phillip, Rosenzweig Bart, Hoffmann Norah M, Lacombe Lionel, Maitra Neepa T
Department of Physics and Astronomy, Hunter College of the City University of New York, 695 Park Avenue, New York, New York 10065, USA.
Department of Physics, Rutgers University, Newark, New Jersey 07102, USA.
J Chem Phys. 2021 Jan 7;154(1):014102. doi: 10.1063/5.0033386.
The exact time-dependent potential energy surface driving the nuclear dynamics was recently shown to be a useful tool to understand and interpret the coupling of nuclei, electrons, and photons in cavity settings. Here, we provide a detailed analysis of its structure for exactly solvable systems that model two phenomena: cavity-induced suppression of proton-coupled electron-transfer and its dependence on the initial state, and cavity-induced electronic excitation. We demonstrate the inadequacy of simply using a weighted average of polaritonic surfaces to determine the dynamics. Such a weighted average misses a crucial term that redistributes energy between the nuclear and the polaritonic systems, and this term can in fact become a predominant term in determining the nuclear dynamics when several polaritonic surfaces are involved. Evolving an ensemble of classical trajectories on the exact potential energy surface reproduces the nuclear wavepacket quite accurately, while evolving on the weighted polaritonic surface fails after a short period of time. The implications and prospects for application of mixed quantum-classical methods based on this surface are discussed.
最近研究表明，驱动核动力学的精确含时势能面是理解和解释腔环境中原子核、电子和光子耦合的有用工具。在此，我们对其结构进行详细分析，针对能够模拟两种现象的精确可解系统：腔诱导的质子耦合电子转移抑制及其对初始状态的依赖性，以及腔诱导的电子激发。我们证明了简单使用极化子表面的加权平均值来确定动力学是不够的。这样的加权平均值遗漏了一个在核系统和极化子系统之间重新分配能量的关键项，当涉及多个极化子表面时，该项实际上可能成为决定核动力学的主导项。在精确势能面上演化一组经典轨迹能够相当准确地重现核波包，而在加权极化子表面上演化则在短时间后失效。本文还讨论了基于该表面的混合量子 - 经典方法的应用意义和前景。
