Acceleration

Electrical engineering

Physics

Kinetics

Transition state theory

Mechanics

Redistribution (election)

Politics

Engineering

Coupling (piping)

Catalysis

Reaction rate

Political science

Computational chemistry

Reaction coordinate

Chemical physics

Chemistry

Metallurgy

Materials science

Thermal

Condensed matter physics

Molecular physics

Transmission coefficient

Coupling strength

Biochemistry

Classical mechanics

Transmission (telecommunications)

Reaction rate constant

Thermodynamics

The Journal of Physical Chemistry Letters

The observed modification of thermal chemical rates in Fabry-Perot cavities remains a poorly understood effect theoretically. Recent breakthroughs explain some of the observations through the Grote-Hynes theory, where the cavity introduces friction with the reaction coordinate, thus reducing the transmission coefficient and the rate. The regime of rate enhancement, the observed sharp resonances at varying cavity frequencies, and the survival of these effects in the collective regime remain mostly unexplained. In this Letter, we consider the cis-trans isomerization of HONO atomistically using an ab initio potential energy surface. We evaluate the transmission coefficient using the reactive flux method and identify the conditions for rate acceleration. In the underdamped, low-friction regime of the reaction coordinate, the cavity coupling enhances the rate with increasing coupling strength until reaching the Kramers turnover point. Sharp resonances in this regime are related to cavity-enabled energy redistribution channels.

Suppression and Enhancement of Thermal Chemical Rates in a Cavity