Saller Maximlian A C, Lai Yifan, Geva Eitan
Department of Chemistrty, University of Michigan, Ann Arbor, Michigan 48109, USA.
Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.
J Chem Phys. 2023 Oct 21;159(15). doi: 10.1063/5.0172265.
We extend our recently proposed theoretical framework for estimating cavity-modified equilibrium Fermi's golden rule (FGR) rate constants beyond the single cavity mode case to cases where the molecular system is coupled to multiple cavity modes. We show that the cumulative effect of simultaneous coupling to multiple modes can enhance FGR rate constants by orders of magnitude relative to the single mode case. We also present an analysis of the conditions necessary for maximizing this effect in the Marcus limit of FGR-based rate theory.
我们将最近提出的用于估计腔修正平衡费米黄金规则（FGR）速率常数的理论框架从单腔模情况扩展到分子系统耦合到多个腔模的情况。我们表明，相对于单模情况，同时耦合到多个模的累积效应可将FGR速率常数提高几个数量级。我们还对基于FGR的速率理论的马库斯极限中最大化此效应所需的条件进行了分析。
