Cavity-modified Fermi’s golden rule rate constants: Beyond the single mode approximation
Maximilian A. C. Saller, Yifan Lai, Eitan Geva
Abstract
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.
Topics & Concepts
Fermi's golden ruleMode (computer interface)Reaction rate constantCoupling constantChemistryLimit (mathematics)Fermi Gamma-ray Space TelescopeCoupling (piping)Statistical physicsThermodynamicsPhysicsAtomic physicsQuantum mechanicsMaterials scienceKineticsMathematicsMathematical analysisMetallurgyComputer scienceOperating systemStrong Light-Matter InteractionsSpectroscopy and Quantum Chemical StudiesMolecular Junctions and Nanostructures