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Abstract Recent experiments demonstrate the control of chemical reactivities by coupling molecules inside an optical microcavity. In contrast, transition state theory predicts no change of the reaction barrier height during this process. Here, we present a theoretical explanation of the cavity modification of the ground state reactivity in the vibrational strong coupling (VSC) regime in polariton chemistry. Our theoretical results suggest that the VSC kinetics modification is originated from the non-Markovian dynamics of the cavity radiation mode that couples to the molecule, leading to the dynamical caging effect of the reaction coordinate and the suppression of reaction rate constant for a specific range of photon frequency close to the barrier frequency. We use a simple analytical non-Markovian rate theory to describe a single molecular system coupled to a cavity mode. We demonstrate the accuracy of the rate theory by performing direct numerical calculations of the transmission coefficients with the same model of the molecule-cavity hybrid system. Our simulations and analytical theory provide a plausible explanation of the photon frequency dependent modification of the chemical reactivities in the VSC polariton chemistry.
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The orientation dependence of cavity-modified chemistry
Recent theoretical studies have explored how ultra-strong light–matter coupling can be used as a handle to control chemical transformations. Ab initio cavity quantum electrodynamics calculations demonstrate that large changes to reaction energies or barrier heights can be realized by coupling electronic degrees of freedom to vacuum fluctuations associated with an optical cavity mode, provided that large enough coupling strengths can be achieved. In many cases, the cavity effects display a pronounced orientational dependence. Here, we highlight the critical role that geometry relaxation can play in such studies. As an example, we consider a recent work [Pavošević et al., Nat. Commun. 14, 2766 (2023)] that explored the influence of an optical cavity on Diels–Alder cycloaddition reactions and reported large changes to reaction enthalpies and barrier heights, as well as the observation that changes in orientation can inhibit the reaction or select for one reaction product or another. Those calculations used fixed molecular geometries optimized in the absence of the cavity and fixed relative orientations of the molecules and the cavity mode polarization axis. Here, we show that when given a chance to relax in the presence of the cavity, the molecular species reorient in a way that eliminates the orientational dependence. Moreover, in this case, we find that qualitatively different conclusions regarding the impact of the cavity on the thermodynamics of the reaction can be drawn from calculations that consider relaxed vs unrelaxed molecular structures.
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- Award ID(s):
- 2100984
- PAR ID:
- 10595811
- Publisher / Repository:
- Journal of Chemical Physics
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 161
- Issue:
- 6
- ISSN:
- 0021-9606
- Page Range / eLocation ID:
- 064109
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1063/5.0216993
