On the origin of ground-state vacuum-field catalysis: Equilibrium consideration

Tao E. Li*, Abraham Nitzan, Joseph E. Subotnik

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


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.

Original languageEnglish
Article number234107
JournalJournal of Chemical Physics
Issue number23
StatePublished - 21 Jun 2020


FundersFunder number
Vagelos Institute for Energy Science and Technology
U.S. Department of EnergyDE-AC02-05CH11231
Office of Science
Basic Energy SciencesDE-SC0019397
University of Pennsylvania
Chemical Sciences, Geosciences, and Biosciences Division


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