Multiscale Molecular Dynamics Simulations of Polaritonic Chemistry
Luk, H. L., Feist, J., Toppari, J., & Groenhof, G. (2017). Multiscale Molecular Dynamics Simulations of Polaritonic Chemistry. Journal of Chemical Theory and Computation, 13(9), 4324-4335. https://doi.org/10.1021/acs.jctc.7b00388
Published inJournal of Chemical Theory and Computation
© 2017 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by the American Chemical Society. Published in this repository with the kind permission of the publisher.
When photoactive molecules interact strongly with confined light modes as found in plasmonic structures or optical cavities, new hybrid light-matter states can form, the so-called polaritons. These polaritons are coherent superpositions (in the quantum mechanical sense) of excitations of the molecules and of the cavity photon or surface plasmon. Recent experimental and theoretical works suggest that access to these polaritons in cavities could provide a totally new and attractive paradigm for controlling chemical reactions that falls in between traditional chemical catalysis and coherent laser control. However, designing cavity parameters to control chemistry requires a theoretical model with which the effect of the light-matter coupling on the molecular dynamics can be predicted accurately. Here we present a multiscale quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulation model for photoactive molecules that are strongly coupled to confined light in optical cavities or surface plasmons. Using this model we have performed simulations with up to 1600 Rhodamine molecules in a cavity. The results of these simulations reveal that the contributions of the molecules to the polariton are time-dependent due to thermal fluctuations that break symmetry. Furthermore, the simulations suggest that in addition to the cavity quality factor, also the Stokes shift and number of molecules control the lifetime of the polariton. Because large numbers of molecules interacting with confined light can now be simulated in atomic detail, we anticipate that our method will lead to a better understanding of the effects of strong coupling on chemical reactivity. Ultimately the method may even be used to systematically design cavities to control photochemistry. ...
PublisherAmerican Chemical Society
Publication in research information system
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Related funder(s)Academy of Finland
Funding program(s)Research post as Academy Research Fellow, AoF; Academy Project, AoF
Additional information about fundingThis work was supported by the Academy of Finland (Grants 289947 to J.T.T. and 290677 and 258806 to G.G.) as well as the European Research Council (ERC-2011-AdG-290981) and the European Union Seventh Framework Programme (FP7-PEOPLE-2013-CIG-618229, J.F.). We acknowledge the Center for Scientific Computing (CSC-IT Center for Science) for computational resources. Finally, we acknowledge PRACE for awarding us access to resource Curie based in France at GENCI. ...
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