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Collective Vibrational Strong Coupling Effects on Molecular Vibrational Relaxation and Energy Transfer: Numerical Insights via Cavity Molecular Dynamics Simulations **
Author(s) -
Li Tao E.,
Nitzan Abraham,
Subotnik Joseph E.
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202103920
Subject(s) - excited state , vibrational energy relaxation , chemical physics , relaxation (psychology) , polariton , intermolecular force , molecule , non equilibrium thermodynamics , molecular physics , coupling (piping) , molecular dynamics , molecular vibration , chemistry , atomic physics , materials science , physics , computational chemistry , condensed matter physics , thermodynamics , psychology , social psychology , organic chemistry , metallurgy
For a small fraction of hot CO 2 molecules immersed in a liquid‐phase CO 2 thermal bath, classical cavity molecular dynamics simulations show that forming collective vibrational strong coupling (VSC) between the C=O asymmetric stretch of CO 2 molecules and a cavity mode accelerates hot‐molecule relaxation. This acceleration stems from the fact that polaritons can be transiently excited during the nonequilibrium process, which facilitates intermolecular vibrational energy transfer. The VSC effects on these rates 1) resonantly depend on the cavity mode detuning, 2) cooperatively depend on Rabi splitting, and 3) collectively scale with the number of hot molecules. For larger cavity volumes, the average VSC effect per molecule can remain meaningful for up to N ≈10 4 molecules forming VSC. Moreover, the transiently excited lower polariton prefers to relax by transferring its energy to the tail of the molecular energy distribution rather than distributing it equally to all thermal molecules. As far as the parameter dependence is concerned, the vibrational relaxation data presented here appear analogous to VSC catalysis in Fabry–Pérot microcavities.