Observation of the sub-100 femtosecond population of a dark state in a thiobase mediating intersystem crossing

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dc.creatorRocio Borrego Varillas
dc.creatorDanielle Cristina Teles Ferreira
dc.creatorArtur Nenov
dc.creatorIrene Conti
dc.creatorLucia Ganzer
dc.creatorCristian Manzoni
dc.creatorMarco Garavelli
dc.creatorAna Maria de Paula
dc.creatorGiulio Cerullo
dc.date.accessioned2023-02-14T17:05:59Z
dc.date.accessioned2025-09-08T23:38:35Z
dc.date.available2023-02-14T17:05:59Z
dc.date.issued2018-10-31
dc.description.sponsorshipCNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico
dc.description.sponsorshipFAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais
dc.description.sponsorshipCAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
dc.identifier.doihttps://doi.org/10.1021/jacs.8b07057
dc.identifier.issn1520-5126
dc.identifier.urihttps://hdl.handle.net/1843/50201
dc.languageeng
dc.publisherUniversidade Federal de Minas Gerais
dc.rightsAcesso Restrito
dc.subjectAbsorção
dc.subjectNíveis de energia
dc.subjectOscilações
dc.subject.otherAbsorção
dc.subject.otherNíveis de energia
dc.subject.otherOscilações
dc.titleObservation of the sub-100 femtosecond population of a dark state in a thiobase mediating intersystem crossing
dc.typeArtigo de periódico
local.citation.epage16093
local.citation.issue47
local.citation.spage16087
local.citation.volume140
local.description.resumoWe combined sub-30 fs broadband transient absorption spectroscopy in the ultraviolet with state-of-the-art quantum mechanics/molecular mechanics simulations to study the ultrafast excited-state dynamics of the sulfur-substituted nucleobase 4-thiouracil. We observed a clear mismatch between the time scales for the decay of the stimulated emission from the bright ππ* state (76 ± 16 fs, experimentally elusive until now) and the buildup of the photoinduced absorption of the triplet state (225 ± 30 fs). These data provide evidence that the intersystem crossing occurs via a dark state, which is intermediately populated on the sub-100 fs time scale. Nonlinear spectroscopy simulations, extrapolated from a detailed CASPT2/MM decay path topology of the solvated system together with an excited state mixed quantum-classical nonadiabatic dynamics, reproduce the experimental results and explain the experimentally observed vibrational coherences. The theoretical analysis rationalizes the observed different triplet buildup times of 4- and 2-thiouracil.
local.identifier.orcidhttps://orcid.org/0000-0002-4499-0558
local.identifier.orcidhttps://orcid.org/0000-0001-8001-4709
local.identifier.orcidhttps://orcid.org/0000-0003-3071-5341
local.identifier.orcidhttps://orcid.org/0000-0001-7982-4480
local.identifier.orcidhttps://orcid.org/0000-0002-4169-8869
local.identifier.orcidhttps://orcid.org/0000-0002-0796-289X
local.identifier.orcidhttps://orcid.org/0000-0002-8551-5948
local.identifier.orcidhttps://orcid.org/0000-0002-9534-2702
local.publisher.countryBrasil
local.publisher.departmentICX - DEPARTAMENTO DE FÍSICA
local.publisher.initialsUFMG
local.url.externahttps://pubs.acs.org/doi/10.1021/jacs.8b07057

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