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dc.contributor.authorLin, Zhou
dc.contributor.authorKohn, Alexander W
dc.contributor.authorVan Voorhis, Troy
dc.date.accessioned2022-03-21T18:51:01Z
dc.date.available2022-03-21T18:51:01Z
dc.date.issued2020
dc.identifier.urihttps://hdl.handle.net/1721.1/141335
dc.description.abstractCopyright © 2020 American Chemical Society. Boron-dipyrromethene (BODIPY) molecules are widely used as laser dyes and have therefore become a popular research topic within recent years. Numerous studies have been reported for the rational design of BODIPY derivatives based on their photophysical properties, including absorption and fluorescence wavelengths (λabs and λfl), oscillator strength (f), nonradiative pathways, and quantum yield (φ). In the present work, we illustrate a theoretical, semiempirical model that accurately predicts φ for various BODIPY compounds on the basis of inexpensive electronic structure calculations, following the data-driven algorithm proposed by us in a previous study [ Kohn et al. J. Phys. Chem. C. 2019, 123, 15394[. The model allows us to identify the dominant nonradiative channel of any BODIPY molecule using its structure exclusively and to establish a correlation between the activation energy (Ea) and the fluorescence quantum yield (φfl). On the basis of our calculations, either the S1 → S0 or La → Lb internal conversion (IC) mechanism dominates in the majority of BODIPY derivatives, depending on the structural and electronic properties of the substituents. In either case, the nonradiative rate (knr) exhibits a straightforward Arrhenius-like relation with the associated Ea. More interestingly, the S1 → S0 mechanism proceeds via a highly distorted intermediate structure in which the core BODIPY plane and the substituent at the 1-position are twisted, while the internal rotation of the very same substituent induces the La → Lb transition. Our model reproduces kfl, knr, and φfl to mean absolute errors (MAEs) of 0.16 decades, 0.87 decades, and 0.26, when all outliers are considered. These results allow us to validate the predictive power of the proposed data-driven algorithm in φfl. They also indicate that the model has a great potential to facilitate and accelerate the machine learning aided design of BODIPY dyes for imaging and sensing applications, given sufficient experimental data and appropriate molecular descriptors.en_US
dc.language.isoen
dc.publisherAmerican Chemical Society (ACS)en_US
dc.relation.isversionof10.1021/ACS.JPCC.9B08292en_US
dc.rightsCreative Commons Attribution-Noncommercial-Share Alikeen_US
dc.rights.urihttp://creativecommons.org/licenses/by-nc-sa/4.0/en_US
dc.sourceOther repositoryen_US
dc.titleToward Prediction of Nonradiative Decay Pathways in Organic Compounds II: Two Internal Conversion Channels in BODIPYsen_US
dc.typeArticleen_US
dc.identifier.citationLin, Zhou, Kohn, Alexander W and Van Voorhis, Troy. 2020. "Toward Prediction of Nonradiative Decay Pathways in Organic Compounds II: Two Internal Conversion Channels in BODIPYs." Journal of Physical Chemistry C, 124 (7).
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemistry
dc.relation.journalJournal of Physical Chemistry Cen_US
dc.eprint.versionOriginal manuscripten_US
dc.type.urihttp://purl.org/eprint/type/JournalArticleen_US
eprint.statushttp://purl.org/eprint/status/NonPeerRevieweden_US
dc.date.updated2022-03-21T18:34:35Z
dspace.orderedauthorsLin, Z; Kohn, AW; Van Voorhis, Ten_US
dspace.date.submission2022-03-21T18:34:47Z
mit.journal.volume124en_US
mit.journal.issue7en_US
mit.licenseOPEN_ACCESS_POLICY
mit.metadata.statusAuthority Work and Publication Information Neededen_US


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