Competition between collective and individual conical intersection dynamics in an optical cavity
Light-induced nonadiabatic phenomena arise when molecules or molecular ensembles are exposed to resonant external electromagnetic fields. The latter can either be classical laser or quantized cavity radiation fields, which can couple to either the electronic, nuclear or rotational degrees of freedom...
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| Format: | Article |
| Language: | English |
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IOP Publishing
2022-01-01
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| Series: | New Journal of Physics |
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| Online Access: | https://doi.org/10.1088/1367-2630/ac7df7 |
| _version_ | 1797748349509566464 |
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| author | András Csehi Oriol Vendrell Gábor J Halász Ágnes Vibók |
| author_facet | András Csehi Oriol Vendrell Gábor J Halász Ágnes Vibók |
| author_sort | András Csehi |
| collection | DOAJ |
| description | Light-induced nonadiabatic phenomena arise when molecules or molecular ensembles are exposed to resonant external electromagnetic fields. The latter can either be classical laser or quantized cavity radiation fields, which can couple to either the electronic, nuclear or rotational degrees of freedom of the molecule. In the case of quantized radiation fields, the light–matter coupling results in the formation of two new hybrid light–matter states, namely the upper and lower ‘polaritons’. Light-induced avoided crossings and light-induced conical intersections (CIs) between polaritons exist as a function of the vibrational and rotational coordinates of single molecules. For ensembles of N molecules, the N − 1 dark states between the two optically active polaritons feature, additionally, so-called collective CIs, involving the coordinates of more than one molecule to form. Here, we study the competition between intramolecular and collective light-induced nonadiabatic phenomena by comparing the escape rate from the Franck–Condon region of a single molecule and of a molecular ensemble coupled to a cavity mode. In situations where the polaritonic gap would be large and the dark-state decay channels could not be reached effectively, the presence of a seam of light-induced CI between the polaritons facilitates again the participation of the dark manifold, resulting in a cooperative effect that determines the overall non-radiative decay rate from the upper into the lower polaritonic states. |
| first_indexed | 2024-03-12T16:04:26Z |
| format | Article |
| id | doaj.art-3f266ac694e249e2822eeceff874de83 |
| institution | Directory Open Access Journal |
| issn | 1367-2630 |
| language | English |
| last_indexed | 2024-03-12T16:04:26Z |
| publishDate | 2022-01-01 |
| publisher | IOP Publishing |
| record_format | Article |
| series | New Journal of Physics |
| spelling | doaj.art-3f266ac694e249e2822eeceff874de832023-08-09T14:26:26ZengIOP PublishingNew Journal of Physics1367-26302022-01-0124707302210.1088/1367-2630/ac7df7Competition between collective and individual conical intersection dynamics in an optical cavityAndrás Csehi0https://orcid.org/0000-0002-8794-6610Oriol Vendrell1https://orcid.org/0000-0003-4629-414XGábor J Halász2https://orcid.org/0000-0002-7010-4302Ágnes Vibók3https://orcid.org/0000-0001-6821-9525Department of Theoretical Physics, Faculty of Science and Technology, University of Debrecen , H-4002 Debrecen, PO Box 400, HungaryTheoretical Chemistry, Institute of Physical Chemistry, Heidelberg University , Im Neuenheimer Feld 229, 69120 Heidelberg, GermanyDepartment of Information Technology, Faculty of Informatics, University of Debrecen , H-4002 Debrecen, PO Box 400, HungaryDepartment of Theoretical Physics, Faculty of Science and Technology, University of Debrecen , H-4002 Debrecen, PO Box 400, Hungary; ELI-ALPS, ELI-HU Non-Profit Ltd. , H-6720 Szeged, Dugonics tér 13, HungaryLight-induced nonadiabatic phenomena arise when molecules or molecular ensembles are exposed to resonant external electromagnetic fields. The latter can either be classical laser or quantized cavity radiation fields, which can couple to either the electronic, nuclear or rotational degrees of freedom of the molecule. In the case of quantized radiation fields, the light–matter coupling results in the formation of two new hybrid light–matter states, namely the upper and lower ‘polaritons’. Light-induced avoided crossings and light-induced conical intersections (CIs) between polaritons exist as a function of the vibrational and rotational coordinates of single molecules. For ensembles of N molecules, the N − 1 dark states between the two optically active polaritons feature, additionally, so-called collective CIs, involving the coordinates of more than one molecule to form. Here, we study the competition between intramolecular and collective light-induced nonadiabatic phenomena by comparing the escape rate from the Franck–Condon region of a single molecule and of a molecular ensemble coupled to a cavity mode. In situations where the polaritonic gap would be large and the dark-state decay channels could not be reached effectively, the presence of a seam of light-induced CI between the polaritons facilitates again the participation of the dark manifold, resulting in a cooperative effect that determines the overall non-radiative decay rate from the upper into the lower polaritonic states.https://doi.org/10.1088/1367-2630/ac7df7conical intersectionsradiation fieldcollective effectlight-induced nonadiabatic phenomena |
| spellingShingle | András Csehi Oriol Vendrell Gábor J Halász Ágnes Vibók Competition between collective and individual conical intersection dynamics in an optical cavity New Journal of Physics conical intersections radiation field collective effect light-induced nonadiabatic phenomena |
| title | Competition between collective and individual conical intersection dynamics in an optical cavity |
| title_full | Competition between collective and individual conical intersection dynamics in an optical cavity |
| title_fullStr | Competition between collective and individual conical intersection dynamics in an optical cavity |
| title_full_unstemmed | Competition between collective and individual conical intersection dynamics in an optical cavity |
| title_short | Competition between collective and individual conical intersection dynamics in an optical cavity |
| title_sort | competition between collective and individual conical intersection dynamics in an optical cavity |
| topic | conical intersections radiation field collective effect light-induced nonadiabatic phenomena |
| url | https://doi.org/10.1088/1367-2630/ac7df7 |
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