Catalysis by Dark States in Vibropolaritonic Chemistry

Abstract

Collective strong coupling between a disordered ensemble of $N$ localized molecular vibrations and a resonant optical cavity mode gives rise to 2 polariton and $N-1\gg 2$ dark modes. Thus, experimental changes in thermally-activated reaction kinetics due to polariton formation appear entropically unlikely and remain a puzzle. Here we show that the overlooked dark modes, while parked at the same energy as bare molecular vibrations, are robustly delocalized across $\sim$2-3 molecules, yielding enhanced channels of vibrational cooling, concomitantly catalyzing a chemical reaction. As an illustration, we theoretically show a $\approx$50\% increase in an electron transfer rate due to enhanced product stabilization. The reported effects can arise when the homogeneous linewidths of the dark modes are smaller than their energy spacings.

References in corpus (18)

• Coherent coupling of molecular resonators with a micro-cavity mode
• Molecular polaritons for controlling chemistry with quantum optics
• Resonant catalysis of thermally-activated chemical reactions via vibrational polaritons
• Quantum theory of collective strong coupling of molecular vibrations with a microcavity mode
• Cavity Casimir-Polder forces and their effects in ground state chemical reactivity
• Coupled Cluster Theory for Molecular Polaritons: Changing Ground and Excited States
• Many-molecule reaction triggered by a single photon in polaritonic chemistry
• Theory of Nanoscale Organic Cavities: The Essential Role of Vibration-Photon Dressed States
• On the Origin of Ground-State Vacuum-Field Catalysis: Equilibrium Consideration
• Collective conical intersections through light-matter coupling in a cavity
• Dark state semilocalization of quantum emitters in a cavity
• Polaritonic normal modes in Transition State Theory
• Manipulating Optical Nonlinearities of Molecular Polaritons by Delocalization
• Disorder-Enhanced and Disorder-Independent Transport with Long-Range Hopping: Application to Molecular Chains in Optical Cavities
• Abundance of cavity-free polaritonic states in resonant materials and nanostructures
• Ensemble-induced strong light-matter coupling of a single quantum emitter
• Nonequilibrium effects of cavity leakage and vibrational dissipation in thermally-activated polariton chemistry
• Three-player polaritons: nonadiabatic fingerprints in an entangled atom-molecule-photon system

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• Quantum dynamics of molecular ensembles coupled with quantum light: Counter-rotating interactions as an essential component
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