A Unified Experimental/Theoretical Description of the Ultrafast Photophysics of Single and Double Thionated Uracils.
CASPT2
QM/MM
conical intersections
thiobases
transient absorption
ultrafast spectroscopy
Journal
Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783
Informations de publication
Date de publication:
02 Jan 2020
02 Jan 2020
Historique:
received:
03
10
2019
pubmed:
22
11
2019
medline:
22
11
2019
entrez:
22
11
2019
Statut:
ppublish
Résumé
Photoinduced processes in thiouracil derivatives have lately attracted considerable attention due to their suitability for innovative biological and pharmacological applications. Here, sub-20 fs broadband transient absorption spectroscopy in the near-UV are combined with CASPT2/MM decay path calculations to unravel the excited-state decay channels of water solvated 2-thio and 2,4-dithiouracil. These molecules feature linear absorption spectra with overlapping ππ* bands, leading to parallel decay routes which we systematically track for the first time. The results reveal that different processes lead to the triplet states population, both directly from the ππ* absorbing state and via the intermediate nπ* dark state. Moreover, the 2,4-dithiouracil decay pathways is shown to be strongly correlated either to those of 2- or 4-thiouracil, depending on the sulfur atom on which the electronic transition localizes.
Identifiants
pubmed: 31750960
doi: 10.1002/chem.201904541
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
336-343Subventions
Organisme : Horizon 2020 Framework Programme
ID : Grant No. 654148, Laserlab-Europe
Organisme : H2020 Marie Skłodowska-Curie Actions
ID : 765266
Organisme : European Research Council - Advanced Grant
ID : STRATUS: ERC-2011-AdG No. 291198
Informations de copyright
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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