Saller Maximilian A C, Kelly Aaron, Geva Eitan
Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, United States.
Max Planck Institute for the Structure and Dynamics of Matter, Luruper Chaussee 149, 22761 Hamburg, Germany.
J Phys Chem Lett. 2021 Apr 1;12(12):3163-3170. doi: 10.1021/acs.jpclett.1c00158. Epub 2021 Mar 23.
Recent experimental realizations of strong coupling between optical cavity modes and molecular matter placed inside the cavity have opened exciting new routes for controlling chemical processes. Simulating the cavity-modified dynamics of complex chemical systems calls for the development of accurate, flexible, and cost-effective approximate numerical methods that scale favorably with system size and complexity. In this Letter, we test the ability of quasiclassical mapping Hamiltonian methods to serve this purpose. We simulated the spontaneous emission dynamics of an atom confined to a microcavity via five different variations of the linearized semiclassical (LSC) method. Our main finding is that recently proposed LSC-based methods which use a modified form of the identity operator are reasonably accurate and perform significantly better than the Ehrenfest and standard LSC methods, without significantly increasing computational costs. These methods are therefore highly promising as a general purpose tool for simulating cavity-modified dynamics of complex chemical systems.
近期，光学腔模式与置于腔内的分子物质之间强耦合的实验实现，为控制化学过程开辟了令人兴奋的新途径。模拟复杂化学系统的腔修饰动力学，需要开发精确、灵活且经济高效的近似数值方法，这些方法要能随系统规模和复杂度良好地扩展。在本信函中，我们测试了准经典映射哈密顿方法实现这一目的的能力。我们通过线性化半经典（LSC）方法的五种不同变体，模拟了限制在微腔内的原子的自发发射动力学。我们的主要发现是，最近提出的基于LSC的方法，即使用恒等算子的修正形式，相当准确，并且比埃伦费斯特方法和标准LSC方法表现得明显更好，同时不会显著增加计算成本。因此作为模拟复杂化学系统的腔修饰动力学的通用工具，这些方法极具前景。
