Theoretical formulation of chemical equilibrium under vibrational strong coupling.

ABSTRACT: Experiments have suggested that strong interactions between molecular ensembles and infrared microcavities can be employed to control chemical equilibria. Nevertheless, the primary mechanism and key features of the effect remain largely unexplored. In this work, we develop a theory of chemical equilibrium in optical microcavities, which allows us to relate the equilibrium composition of a mixture in different electromagnetic environments. Our theory shows that in planar microcavities under strong coupling with polyatomic molecules, hybrid modes formed between all dipole-active vibrations and cavity resonances contribute to polariton-assisted chemical equilibrium shifts. To illustrate key aspects of our formalism, we explore a model S_N2 reaction within a single-mode infrared reso

SUBMITTER: Sun K 

PROVIDER: S-EPMC10944518 | biostudies-literature | 2024 Mar

REPOSITORIES: biostudies-literature