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  • Collective Vibrational Strong Coupling Effects on Molecular Vibrational Relaxation and Energy Transfer: Numerical Insights via Cavity Molecular Dynamics Simulations
Title: Collective Vibrational Strong Coupling Effects on Molecular Vibrational Relaxation and Energy Transfer: Numerical Insights via Cavity Molecular Dynamics Simulations
We use classical cavity molecular dynamics simulations to investigate the effect of optical cavity environment on vibrational energy transfer and relaxation. For a small fraction of vibrationally hot CO2 molecules immersed in a liquid-phase CO2 thermal bath, in a cavity that supports a cavity mode in resonance with the CO asymmetric stretch vibration, forming collective vibrational strong coupling (VSC) 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 (i) resonantly depend on the cavity mode detuning, (ii) cooperatively depend on Rabi splitting, and (iii) collectively scale with the number of hot molecules. This behavior weakens with increasing cavity size (at constant molecular density), that is, constant Rabi splitting) but remains meaningful up to cavities containing 10^4 molecules  more » « less
Award ID(s):
1953701
PAR ID:
10251145
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Angewandte Chemie
Volume:
60
ISSN:
1521-3757
Page Range / eLocation ID:
2-10
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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