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dc.contributor.authorKarak, Pijush
dc.contributor.authorRuud, Kenneth
dc.contributor.authorChakrabarti, Swapan
dc.date.accessioned2022-03-04T13:22:11Z
dc.date.available2022-03-04T13:22:11Z
dc.date.issued2021-10-01
dc.description.abstractWe demonstrate that spin-vibronic coupling is the most significant mechanism in vibrational coherence transfer (VCT) from the singlet (S<sub>1</sub>) to the triplet (T<sub>1</sub>) state of the [Pt<sub>2</sub>(P<sub>2</sub>O<sub>5</sub>H<sub>2</sub>)<sub>4</sub>]<sup>4–</sup> complex. Our time-dependent correlation function-based study shows that the rate of intersystem crossing (<i>k</i><sub>ISC</sub>) through direct spin–orbit coupling is negligibly small, making VCT vanishingly small due to the ultrashort decoherence time (2.5 ps). However, the inclusion of the spin-vibronic contribution to the net <i>k</i><sub>ISC</sub> in selective normal modes along the Pt–Pt axis increases the <i>k</i><sub>ISC</sub> to such an extent that VCT becomes feasible. Our results suggest that <i>k</i><sub>ISC</sub> for the S<sub>1</sub> →T<sub>2</sub> (τ<sub>ISC</sub> = 1.084 ps) is much faster than the S<sub>1</sub> → T<sub>1</sub> (τ<sub>ISC</sub> = 763.4 ps) and S<sub>1</sub> → T<sub>3</sub> (τ<sub>ISC</sub> = 13.38 ps) in CH3CN solvent, indicating that VCT is possible from the low-lying excited singlet (S<sub>1</sub>) to the triplet (T<sub>1</sub>) state through the intermediate T<sub>2</sub> state. This is the first example where VCT occurs solely due to spin-vibronic interactions. This finding can pave the way for new types of photocatalysis.en_US
dc.descriptionThis document is the Accepted Manuscript version of a Published Work that appeared in final form in <i>The Journal of Physical Chemistry Letters</i>, copyright © 2021 American Chemical Society after peer review and technical editing by the publisher.en_US
dc.identifier.citationKarak, Ruud, Chakrabarti. Demystifying the Origin of Vibrational Coherence Transfer Between the S1 and T1 States of the Pt-pop Complex. The Journal of Physical Chemistry Letters. 2021:9768-9773en_US
dc.identifier.cristinIDFRIDAID 1951929
dc.identifier.doi10.1021/acs.jpclett.1c02789
dc.identifier.issn1948-7185
dc.identifier.urihttps://hdl.handle.net/10037/24264
dc.language.isoengen_US
dc.publisherACS Publicationsen_US
dc.relation.journalThe Journal of Physical Chemistry Letters
dc.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright 2021 The Author(s)en_US
dc.titleDemystifying the Origin of Vibrational Coherence Transfer Between the S1 and T1 States of the Pt-pop Complexen_US
dc.type.versionacceptedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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