论文标题
腔动力学的时间依赖性势能表面的案例研究
Case Studies of the Time-Dependent Potential Energy Surface for Dynamics in Cavities
论文作者
论文摘要
最近,驱动核动力学的确切时间依赖性势能表面是在空腔设置中理解和解释核,电子和光子偶联的有用工具。在这里,我们为其为恰当可溶的系统提供了详细的分析,该系统对两个现象进行了建模:腔诱导的质子耦合电子传递及其对初始状态的抑制作用以及腔诱导的电子激发。我们证明了简单地使用偏振表面的加权平均值来确定动力学的不足。这样的加权平均值错过了至关重要的术语,即在核系统和极化系统之间重新分布能量,而实际上,当涉及几个极化表面时,该术语实际上可能成为确定核动力学的主要术语。在精确的势能表面上演变的经典轨迹的合奏会非常准确地再现核波袋,而在短时间后在加权极性表面上演变就会失败。讨论了基于该表面的混合量子古典方法的含义和前景。
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.