Resonant Suppression of Local Molecular Vibrations by Cavity-Induced Collective Beating

Recent advances in polaritonic chemistry have suggested the control of chemical reactions through the collective vibrational strong coupling (VSC) of molecules in a cavity [1]. This study investigates the dynamical behavior of a molecular ensemble under VSC, providing a complete analytical classical solution for all degrees of freedom (molecules and cavity). Our findings reveal that under cavity-molecule resonant coupling, collective beatings emerge [2]. The beating period depends on the number of coupled molecules and is significantly longer than the vibrational period of each molecule and of the cavity period. Most importantly, the beating period exhibits a pronounced peak near the cavity-molecule resonance. The collective beating is imprinted in the local dynamics and resonatly suppresses individual molecular vibrations, when the molecules are vibrationally excited, as in activated complexes during a chemical reaction. Our findings offer insights into how collective VSC can resonantly dampen local molecular vibrations, in a clean molecular system, potentially altering chemical reactivity [3].

[1] F. J. Garcia-Vidal, C. Ciuti, T. W. Ebbesen, Science 373,eabd0336(2021)

[2] I. Tutunnikov, V. Rokaj, J. Cao, H. R. Sadeghpour, arXiv:2410.01645 (2024)

[3] V. Rokaj, I. Tutunnikov, H. R. Sadeghpour (2024) [In preparation]