Equilibrium thermodynamics

Quantum mechanics

Context (archaeology)

Reaction rate constant

Catalysis

Thermal equilibrium

Ground state

Chemical physics

Pure mathematics

Biology

Metallurgy

Materials science

Reaction rate

Chemical reaction

Field (mathematics)

Coupling (piping)

Transition state

Atomic physics

Biochemistry

Classical mechanics

Physical chemistry

Paleontology

Photon

Thermodynamics

Physics

Mathematics

Reaction coordinate

Thermal

Chemical equilibrium

Computational chemistry

Kinetics

Chemistry

Transition state theory

Thermodynamic equilibrium

The Journal of Chemical Physics

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.

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