Vibropolaritonic Reaction Rates in the Collective Strong Coupling Regime: Pollak-Grabert-Hänggi Theory

Abstract

Following experimental evidence that vibrational polaritons, formed from collective vibrational strong coupling (VSC) in optical microcavities, can modify ground-state reaction rates, a spate of theoretical explanations relying on cavity-induced frictions has been proposed through the Pollak-Grabert-Hänggi (PGH) theory, which goes beyond transition state theory (TST). However, by considering only a single reacting molecule coupled to light, these works do not capture the ensemble effects present in experiments. Moreover, the relevant light-matter coupling should have been $\sqrt{N}$ times smaller than those used by preceding works, where $N\approx 10^6-10^{12}$ is the ensemble size. In this work, we explain why this distinction is significant and can nullify effects from these cavity-induced frictions. By analytically extending the cavity PGH model to realistic values of $N$, we show how this model succumbs to the polariton "large $N$ problem", that is, the situation whereby the single reacting molecule feels only a tiny $1/N$ part of the collective light-matter interaction intensity, where $N$ is large.

9 pages, 4 figures

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Cited by in corpus (5)

• Swinging between shine and shadow: Theoretical advances on thermally-activated vibropolaritonic chemistry (a perspective)
• Beyond Cavity Born-Oppenheimer: On Non-Adiabatic Coupling and Effective Ground State Hamiltonians in Vibro-Polaritonic Chemistry
• Investigating the Collective Nature of Cavity Modified Chemical Kinetics under Vibrational Strong Coupling
• Understanding the Energy Gap Law under Vibrational Strong Coupling
• Unraveling Abnormal Collective Effects via the Non-Monotonic Number Dependence of Electron Transfer in Confined Electromagnetic Fields