Tracking Polariton Relaxation with Multiscale Molecular Dynamics Simulations
Entity
UAM. Departamento de Física Teórica de la Materia CondensadaPublisher
American Chemical SocietyDate
2019-08-27Citation
10.1021/acs.jpclett.9b02192
Journal of Physical Chemistry Letters 10.18 (2019): 5476-5483
ISSN
1948-7185DOI
10.1021/acs.jpclett.9b02192Funded by
This work was supported by the Academy of Finland (Grants 289947 to JJT, 290677 to GG, and 285481 to DM) as well as the European Research Council (ERC-2016-StG-714870 to JF) and the Spanish Ministry for Science, Innovation, and Universities − AEI (RTI2018-099737-B-I00 to JF). We thank the Center for Scientific Computing (CSC-IT Center for Science) for computational resources and Fredrik Robertsen in particular ́ for his help with running our simulations on GPUs. We also acknowledge PRACE for awarding us access to resource Curie based in France at GENCIProject
info:eu-repo/grantAgreement/EC/H2020/714870/EU//MMUSCLES; Gobierno de España. RTI2018-099737-B-I00Editor's Version
https://doi.org/10.1021/acs.jpclett.9b02192Subjects
Molecular dynamics; Multiscale modeling; Polariton Relaxation; FísicaRights
© 2019 American Chemical SocietyEsta obra está bajo una licencia de Creative Commons Reconocimiento-NoComercial-SinObraDerivada 4.0 Internacional.
Abstract
When photoactive molecules interact strongly with confined light modes in optical cavities, new hybrid light–matter states form. They are known as polaritons and correspond to coherent superpositions of excitations of the molecules and of the cavity photon. The polariton energies and thus potential energy surfaces are changed with respect to the bare molecules, such that polariton formation is considered a promising paradigm for controlling photochemical reactions. To effectively manipulate photochemistry with confined light, the molecules need to remain in the polaritonic state long enough for the reaction on the modified potential energy surface to take place. To understand what determines this lifetime, we have performed atomistic molecular dynamics simulations of room-temperature ensembles of rhodamine chromophores strongly coupled to a single confined light mode with a 15 fs lifetime. We investigated three popular experimental scenarios and followed the relaxation after optically pumping (i) the lower polariton, (ii) the upper polariton, or (iii) uncoupled molecular states. The results of the simulations suggest that the lifetimes of the optically accessible lower and upper polaritons are limited by (i) ultrafast photoemission due to the low cavity lifetime and (ii) reversible population transfer into the “dark” state manifold. Dark states are superpositions of molecular excitations but with much smaller contributions from the cavity photon, decreasing their emission rates and hence increasing their lifetimes. We find that population transfer between polaritonic modes and dark states is determined by the overlap between the polaritonic and molecular absorption spectra. Importantly, excitation can also be transferred ”upward” from the lower polariton into the dark-state reservoir due to the broad absorption spectra of the chromophores, contrary to the common conception of these processes as a ”one-way” relaxation from the dark states down to the lower polariton. Our results thus suggest that polaritonic chemistry relying on modified dynamics taking place within the lower polariton manifold requires cavities with sufficiently long lifetimes and, at the same time, strong light–matter coupling strengths to prevent the back-transfer of excitation into the dark states
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Google Scholar:Groenhof, Gerrit
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Climent, Clàudia
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Feist, Johannes
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Morozov, Dmitry
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Toppari, J. Jussi
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