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• W3100333939 startingPage "234107" @default.
• W3100333939 abstract "Recent experiments suggest that vibrational strong coupling (VSC) may significantly modify ground-state chemical reactions and their rates even without external pumping. The intrinsic mechanism of this vacuum-field catalysis remains largely unclear. Generally, modifications of thermal reactions in the ground electronic states can be caused by equilibrium or non-equilibrium effects. The former are associated with modifications of the reactant equilibrium distribution as expressed by the transition state theory of chemical reaction rates, while the latter stem from the dynamics of reaching and leaving transition state configurations. Here, we examine how VSC can affect chemical reactions rates in a cavity environment according to transition state theory. Our approach is to examine the effect of coupling to cavity mode(s) on the potential of mean force (PMF) associated with the reaction coordinate. Within the context of classical nuclei and classical photons and also assuming no charge overlap between molecules, we find that while the PMF can be affected by the cavity environment, this effect is negligible for the usual micron-length cavities used to examine VSC situations." @default.
• W3100333939 created "2020-11-23" @default.
• W3100333939 creator A5031745251 @default.
• W3100333939 creator A5035641566 @default.
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• W3100333939 date "2020-06-21" @default.
• W3100333939 modified "2023-10-13" @default.
• W3100333939 title "On the origin of ground-state vacuum-field catalysis: Equilibrium consideration" @default.
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• W3100333939 doi "https://doi.org/10.1063/5.0006472" @default.
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• W3100333939 hasPublicationYear "2020" @default.
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