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dc.contributor.authorTichauer, Ruth H.
dc.contributor.authorFeist, Johannes
dc.contributor.authorGroenhof, Gerrit
dc.date.accessioned2021-03-22T08:13:29Z
dc.date.available2021-03-22T08:13:29Z
dc.date.issued2021
dc.identifier.citationTichauer, R. H., Feist, J., & Groenhof, G. (2021). Multi-scale dynamics simulations of molecular polaritons : the effect of multiple cavity modes on polariton relaxation. <i>Journal of Chemical Physics</i>, <i>154</i>(10), Article 104112. <a href="https://doi.org/10.1063/5.0037868" target="_blank">https://doi.org/10.1063/5.0037868</a>
dc.identifier.otherCONVID_51904115
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/74702
dc.description.abstractCoupling molecules to the confined light modes of an optical cavity is showing great promise for manipulating chemical reactions. However, to fully exploit this principle and use cavities as a new tool for controlling chemistry, a complete understanding of the effects of strong light–matter coupling on molecular dynamics and reactivity is required. While quantum chemistry can provide atomistic insight into the reactivity of uncoupled molecules, the possibilities to also explore strongly coupled systems are still rather limited due to the challenges associated with an accurate description of the cavity in such calculations. Despite recent progress in introducing strong coupling effects into quantum chemistry calculations, applications are mostly restricted to single or simplified molecules in ideal lossless cavities that support a single light mode only. However, even if commonly used planar mirror micro-cavities are characterized by a fundamental mode with a frequency determined by the distance between the mirrors, the cavity energy also depends on the wave vector of the incident light rays. To account for this dependency, called cavity dispersion, in atomistic simulations of molecules in optical cavities, we have extended our multi-scale molecular dynamics model for strongly coupled molecular ensembles to include multiple confined light modes. To validate the new model, we have performed simulations of up to 512 Rhodamine molecules in red-detuned Fabry–Pérot cavities. The results of our simulations suggest that after resonant excitation into the upper polariton at a fixed wave vector, or incidence angle, the coupled cavity-molecule system rapidly decays into dark states that lack dispersion. Slower relaxation from the dark state manifold into both the upper and lower bright polaritons causes observable photo-luminescence from the molecule–cavity system along the two polariton dispersion branches that ultimately evolves toward the bottom of the lower polariton branch, in line with experimental observations. We anticipate that the more realistic cavity description in our approach will help to better understand and predict how cavities can modify molecular properties.en
dc.format.mimetypeapplication/pdf
dc.languageeng
dc.language.isoeng
dc.publisherAIP Publishing
dc.relation.ispartofseriesJournal of Chemical Physics
dc.rightsIn Copyright
dc.subject.otherquantum chemistry
dc.subject.otherquantum mechanical/molecular mechanical calculations
dc.subject.othermolecular dynamics
dc.subject.othermolecular properties
dc.subject.otherphotoluminescence
dc.subject.otherdark states
dc.subject.otheratomistic simulations
dc.titleMulti-scale dynamics simulations of molecular polaritons : the effect of multiple cavity modes on polariton relaxation
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-202103222039
dc.contributor.laitosKemian laitosfi
dc.contributor.laitosDepartment of Chemistryen
dc.contributor.oppiaineFysikaalinen kemiafi
dc.contributor.oppiaineNanoscience Centerfi
dc.contributor.oppiainePhysical Chemistryen
dc.contributor.oppiaineNanoscience Centeren
dc.type.urihttp://purl.org/eprint/type/JournalArticle
dc.description.reviewstatuspeerReviewed
dc.relation.issn0021-9606
dc.relation.numberinseries10
dc.relation.volume154
dc.type.versionpublishedVersion
dc.rights.copyright© 2021 Author(s).
dc.rights.accesslevelopenAccessfi
dc.relation.grantnumber323996
dc.subject.ysokvanttikemia
dc.subject.ysofotoluminesenssi
dc.subject.ysopolaritonit
dc.subject.ysomolekyylidynamiikka
dc.format.contentfulltext
jyx.subject.urihttp://www.yso.fi/onto/yso/p19301
jyx.subject.urihttp://www.yso.fi/onto/yso/p26631
jyx.subject.urihttp://www.yso.fi/onto/yso/p38894
jyx.subject.urihttp://www.yso.fi/onto/yso/p29332
dc.rights.urlhttp://rightsstatements.org/page/InC/1.0/?language=en
dc.relation.doi10.1063/5.0037868
dc.relation.funderSuomen Akatemiafi
dc.relation.funderAcademy of Finlanden
jyx.fundingprogramAkatemiahanke, SAfi
jyx.fundingprogramAcademy Project, AoFen
jyx.fundinginformationThis work was supported by the Academy of Finland (Grant No. 323996 to G.G.) as well as the European Research Council (Grant No. ERC-2016-StG714870 to J.F.) and the Spanish Ministry for Science, Innovation, and Universities—AEI (Grant No. RTI2018-099737-B-I00 to J.F.)


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