A1 Journal article (refereed)
Identifying Vibrations that Control Non-adiabatic Relaxation of Polaritons in Strongly Coupled Molecule-Cavity Systems (2022)

Tichauer, R. H., Morozov, D., Sokolovskii, I., Toppari, J. J., & Groenhof, G. (2022). Identifying Vibrations that Control Non-adiabatic Relaxation of Polaritons in Strongly Coupled Molecule-Cavity Systems. Journal of Physical Chemistry Letters, 13(26), 6259-6267. https://doi.org/10.1021/acs.jpclett.2c00826

JYU authors or editors

Publication details

All authors or editors: Tichauer, Ruth H.; Morozov, Dmitry; Sokolovskii, Ilia; Toppari, J. Jussi; Groenhof, Gerrit

Journal or series: Journal of Physical Chemistry Letters

ISSN: 1948-7185

eISSN: 1948-7185

Publication year: 2022

Publication date: 30/06/2022

Volume: 13

Issue number: 26

Pages range: 6259-6267

Publisher: American Chemical Society (ACS)

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1021/acs.jpclett.2c00826

Publication open access: Openly available

Publication channel open access: Partially open access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/82359

Abstract

The strong light–matter coupling regime, in which excitations of materials hybridize with excitations of confined light modes into polaritons, holds great promise in various areas of science and technology. A key aspect for all applications of polaritonic chemistry is the relaxation into the lower polaritonic states. Polariton relaxation is speculated to involve two separate processes: vibrationally assisted scattering (VAS) and radiative pumping (RP), but the driving forces underlying these two mechanisms are not fully understood. To provide mechanistic insights, we performed multiscale molecular dynamics simulations of tetracene molecules strongly coupled to the confined light modes of an optical cavity. The results suggest that both mechanisms are driven by the same molecular vibrations that induce relaxation through nonadiabatic coupling between dark states and polaritonic states. Identifying these vibrational modes provides a rationale for enhanced relaxation into the lower polariton when the cavity detuning is resonant with specific vibrational transitions.

Keywords: energy; molecules; coupling; oscillations

Free keywords: cavities; energy; molecules; nonadiabatic coupling; oscillation

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Ministry reporting: Yes

VIRTA submission year: 2022

JUFO rating: 3