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@ARTICLE{Faccial:639647,
author = {Faccialà, Davide and Bonanomi, Matteo and Tenorio, Bruno
Nunes Cabral and Avaldi, Lorenzo and Bolognesi, Paola and
Callegari, Carlo and Coreno, Marcello and Coriani, Sonia and
Decleva, Piero and Devetta, Michele and Došlić, Nađa and
De Fanis, Alberto and Di Fraia, Michele and Lever, Fabiano
and Mazza, Tommaso and Meyer, Michael and Mullins, Terry and
Ovcharenko, Yevheniy and Pal, Nitish and Piancastelli, Maria
Novella and Richter, Robert and Rivas, Daniel E. and
Sapunar, Marin and Senfftleben, Björn and Usenko, Sergey
and Vozzi, Caterina and Gühr, Markus and Prince, Kevin and
Plekan, Oksana},
title = {{U}nraveling the {R}elaxation {D}ynamics of {U}racil:
{I}nsights from {T}ime-{R}esolved {X}-ray {P}hotoelectron
{S}pectroscopy},
journal = {Journal of the American Chemical Society},
volume = {147},
number = {34},
issn = {0002-7863},
address = {Washington, DC},
publisher = {ACS Publications},
reportid = {PUBDB-2025-04604},
pages = {30694 - 30707},
year = {2025},
note = {cc-by},
abstract = {We report a study of the electronic and nuclear relaxation
dynamics of the photoexcited RNA base uracil in the gas
phase using time-resolved core-level photoelectron
spectroscopy together with high-level calculations. The
dynamics was investigated by trajectory surface hopping
calculations, and the core ionization energies were
calculated for geometries sampled from these. The molecule
was excited by a UV laser and dynamics probed on the oxygen,
nitrogen, and carbon sites by core electron spectroscopy. We
find that the main de-excitation channel of the initially
excited S2(ππ*) state involves internal conversion to the
S1(nπ*) state with a time constant of 17 ± 4 fs, while a
portion of S2(ππ*) population returns directly to the
ground state by internal conversion. We find no evidence
that the S1(nπ*) state decays to the ground state; instead,
it decays to triplet states with a time constant of 1.6 ±
0.4 ps. Oscillations of the S1(nπ*) state O 1s intensity as
a function of time correlate with those of calculated
C4═O8 and C5═C6 bond lengths, which undergo a sudden
expansion following the initial π → π* excitation. Our
calculations support our interpretation of the data and
provide detailed insight into the relaxation processes of
uracil.},
cin = {FS-FLASH},
ddc = {540},
cid = {I:(DE-H253)FS-FLASH-20140814},
pnm = {632 - Materials – Quantum, Complex and Functional
Materials (POF4-632) / TR-AES - Theoretical beamlines to
time-resolved ultrafast Auger electron spectroscopy
(101027796)},
pid = {G:(DE-HGF)POF4-632 / G:(EU-Grant)101027796},
experiment = {EXP:(DE-H253)XFEL-SQS-20150101},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:40802197},
doi = {10.1021/jacs.5c04874},
url = {https://bib-pubdb1.desy.de/record/639647},
}