论文标题
用于模拟极化化学的准绝热繁殖方案
Quasi-Diabatic Propagation Scheme for Simulating Polariton Chemistry
论文作者
论文摘要
我们概括了准绝热（QD）的传播方案，以模拟分子 - 腔杂种系统中的非绝热极化动力学。绝热状态是该分子和光子斑状态的绝热电子状态的张量状态，被用作动力学繁殖的局部定义良好的绝症状态。这些局部定义明确的绝热状态允许使用任何具有绝热的量子动力学方法进行动力传播，并且这些状态的定义将在每个核时间步骤中进行更新。我们使用几种最近开发的非绝热映射方法作为绝热动力学方法，以模拟与光腔相连的Shin-metiu模型中的极化量子量子动力学。与数值精确的方法相比，从映射方法获得的结果提供了非常准确的种群动力学，并且胜过广泛使用的混合量子古典方法，例如Ehrenfest动力学和最少的开关表面跳跃方法。我们设想，这项工作中开发的广义QD方案将提供强大的工具来执行非绝热偏光子模拟，通过允许在糖尿病动力学方法和从头启动极性信息之间进行直接接口。
We generalize the quasi-diabatic (QD) propagation scheme to simulate the non-adiabatic polariton dynamics in molecule-cavity hybrid systems. The adiabatic-Fock states, which are the tensor product states of the adiabatic electronic states of the molecule and photon Fock states, are used as the locally well-defined diabatic states for the dynamics propagation. These locally well-defined diabatic states allow using any diabatic quantum dynamics methods for dynamics propagation, and the definition of these states will be updated at every nuclear time step. We use several recently developed non-adiabatic mapping approaches as the diabatic dynamics methods to simulate polariton quantum dynamics in a Shin-Metiu model coupled to an optical cavity. The results obtained from the mapping approaches provide very accurate population dynamics compared to the numerically exact method and outperform the widely used mixed quantum-classical approaches, such as the Ehrenfest dynamics and the fewest switches surface hopping approach. We envision that the generalized QD scheme developed in this work will provide a powerful tool to perform the non-adiabatic polariton simulations by allowing a direct interface between the diabatic dynamics methods and ab initio polariton information.
