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@ARTICLE{Borne:605377,
author = {Borne, Kurtis D. and Cooper, Joseph C. and ashfold, michael
and Bachmann, Julien and Bhattacharyya, Surjendu and Boll,
Rebecca and Bonanomi, Matteo and Bosch, Michael and
Callegari, Carlo and Centurion, Martin and Coreno, Marcello
and Curchod, Basile and Danailov, Miltcho B. and Demidovich,
Alexander and Di Fraia, Michele and Erk, Benjamin and
Facciala, Davide and Feifel, Raimund and Forbes, Ruaridh and
Hansen, Christopher and Holland, David and Ingle, Rebecca
and Lindh, Roland and Ma, Lingyu and McGhee, Henry G. and
Muvva, Sri Bhavya and Nunes, Joao Pedro Figueira and Odate,
Asami and Pathak, Shashank and Plekan, Oksana and Prince,
Kevin and Rebernik, Primoz and Rouzée, Arnaud and Rudenko,
Artem and Simoncig, Alberto and Squibb, Richard and
Venkatachalam, Anbu and Vozzi, Caterina and Weber, Peter M.
and Kirrander, Adam and Rolles, Daniel},
title = {{U}ltrafast electronic relaxation pathways of the molecular
photoswitch quadricyclane},
journal = {Nature chemistry},
volume = {16},
number = {4},
issn = {1755-4330},
address = {London},
publisher = {Nature Publishing Group},
reportid = {PUBDB-2024-01444},
pages = {499-505},
year = {2024},
abstract = {The light-induced ultrafast switching between molecular
isomers norbornadiene and quadricyclane can reversibly store
and release a substantial amount of chemical energy. Prior
work observed signatures of ultrafast molecular dynamics in
both isomers upon ultraviolet excitation but could not
follow the electronic relaxation all the way back to the
ground state experimentally. Here we study the electronic
relaxation of quadricyclane after exciting in the
ultraviolet (201 nanometres) using time-resolved gas-phase
extreme ultraviolet photoelectron spectroscopy combined with
non-adiabatic molecular dynamics simulations. We identify
two competing pathways by which electronically excited
quadricyclane molecules relax to the electronic ground
state. The fast pathway (<100 femtoseconds) is
distinguished by effective coupling to valence electronic
states, while the slow pathway involves initial motions
across Rydberg states and takes several hundred
femtoseconds. Both pathways facilitate interconversion
between the two isomers, albeit on different timescales, and
we predict that the branching ratio of
norbornadiene/quadricyclane products immediately after
returning to the electronic ground state is approximately
3:2.},
cin = {FS-FLASH-O / $XFEL_E2_SQS$},
ddc = {540},
cid = {I:(DE-H253)FS-FLASH-O-20160930 /
$I:(DE-H253)XFEL_E2_SQS-20210408$},
pnm = {631 - Matter – Dynamics, Mechanisms and Control
(POF4-631)},
pid = {G:(DE-HGF)POF4-631},
experiment = {EXP:(DE-MLZ)External-20140101},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:38307994},
UT = {WOS:001156518100001},
doi = {10.1038/s41557-023-01420-w},
url = {https://bib-pubdb1.desy.de/record/605377},
}