Nonadiabatic phenomena are investigated in the rovibrational motion of molecules confined in an infrared cavity. Conical intersections (CIs) between vibrational polaritons, similar to CIs between electronic polaritonic surfaces, are found. The spectral, topological, and dynamic properties of the vibrational polaritons show clear fingerprints of nonadiabatic couplings between molecular vibration, rotation, and the cavity photonic mode. Furthermore, it is found that for the investigated system, composed of two rovibrating HCl molecules and the cavity mode, breaking the molecular permutational symmetry, by changing Cl to Cl in one of the HCl molecules, the polaritonic surfaces, nonadiabatic couplings, and related spectral, topological, and dynamic properties can deviate substantially. This implies that the natural occurrence of different molecular isotopologues needs to be considered when modeling realistic polaritonic systems.
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14 February 2021
Research Article|
February 11 2021
Nonadiabatic phenomena in molecular vibrational polaritons
Special Collection:
Polariton Chemistry: Molecules in Cavities and Plasmonic Media
Tamás Szidarovszky
;
Tamás Szidarovszky
a)
1
Institute of Chemistry, ELTE Eötvös Loránd University and MTA-ELTE Complex Chemical Systems Research Group
, Pázmány Péter sétány 1/A, H-1117 Budapest, Hungary
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Péter Badankó;
Péter Badankó
2
Department of Theoretical Physics, University of Debrecen
, P.O. Box 400, H-4002 Debrecen, Hungary
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Gábor J. Halász
;
Gábor J. Halász
3
Department of Information Technology, University of Debrecen
, P.O. Box 400, H-4002 Debrecen, Hungary
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Ágnes Vibók
Ágnes Vibók
b)
2
Department of Theoretical Physics, University of Debrecen
, P.O. Box 400, H-4002 Debrecen, Hungary
4
ELI-ALPS, ELI-HU Non-Profit Ltd.
, Dugonics tér 13, H-6720 Szeged, Hungary
b)Author to whom correspondence should be addressed: vibok@phys.unideb.hu
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b)Author to whom correspondence should be addressed: vibok@phys.unideb.hu
Note: This paper is part of the JCP Special Topic on Polariton Chemistry: Molecules in Cavities and Plasmonic Media.
J. Chem. Phys. 154, 064305 (2021)
Article history
Received:
October 16 2020
Accepted:
January 11 2021
Citation
Tamás Szidarovszky, Péter Badankó, Gábor J. Halász, Ágnes Vibók; Nonadiabatic phenomena in molecular vibrational polaritons. J. Chem. Phys. 14 February 2021; 154 (6): 064305. https://doi.org/10.1063/5.0033338
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