Shake-Down Spectroscopy as State- and Site-Specific Probe of Ultrafast Chemical Dynamics
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F25%3A10510772" target="_blank" >RIV/00216208:11320/25:10510772 - isvavai.cz</a>
Result on the web
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=0br_xGMT0B" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=0br_xGMT0B</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/jacs.5c09162" target="_blank" >10.1021/jacs.5c09162</a>
Alternative languages
Result language
angličtina
Original language name
Shake-Down Spectroscopy as State- and Site-Specific Probe of Ultrafast Chemical Dynamics
Original language description
Tracking the multifarious ultrafast electronic and structural changes occurring in a molecule during a photochemical transformation is a challenging endeavor that benefits from recent experimental and computational progress in time-resolved techniques. Measurements of valence electronic states, which provide a global picture of the bonding structure of the molecule, and core electronic states, which provide insight into the local environment, traditionally require different approaches and are often studied separately. Here, we demonstrate that X-ray pulses from a seeded free-electron laser (FEL) enable the measurement of high-resolution, time-resolved X-ray photoelectron spectra (XPS) that capture weak satellite states resulting from shake-down processes in a valence-excited molecule. This approach effectively combines the advantages of both valence- and core-state investigations. We applied this method to investigate photoexcited CS2 molecules, where the role of internal conversion (IC) and intersystem crossing (ISC) in determining the predissociation dynamics is controversial. We present XPS spectra from photoexcited CS2, obtained at the FERMI FEL. High-resolution measurements, compared to the corresponding spectra obtained from accurate multireference quantum chemical calculations, reveal that shake-down satellite channels are highly sensitive to both valence electronic and geometric changes. Previous studies of the predissociation dynamics have led to uncertain assignments of the branching between singlet and triplet excited states. We derive a propensity rule that demonstrates the spin-selectivity of the shake-downs. This selectivity allows us to unequivocally assign contributions from the bright and dark singlet excited states, with populations tracked along the predissociation dynamic pathway.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10305 - Fluids and plasma physics (including surface physics)
Result continuities
Project
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Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of the American Chemical Society
ISSN
0002-7863
e-ISSN
1520-5126
Volume of the periodical
147
Issue of the periodical within the volume
36
Country of publishing house
US - UNITED STATES
Number of pages
10
Pages from-to
32851-32860
UT code for WoS article
001562266600001
EID of the result in the Scopus database
2-s2.0-105015359507