On the Wavelength-Dependent Photochemistry of the Atmospheric Molecule CF3COCl
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F23%3A43928103" target="_blank" >RIV/60461373:22340/23:43928103 - isvavai.cz</a>
Result on the web
<a href="https://pubs.acs.org/doi/10.1021/acsearthspacechem.3c00196" target="_blank" >https://pubs.acs.org/doi/10.1021/acsearthspacechem.3c00196</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acsearthspacechem.3c00196" target="_blank" >10.1021/acsearthspacechem.3c00196</a>
Alternative languages
Result language
angličtina
Original language name
On the Wavelength-Dependent Photochemistry of the Atmospheric Molecule CF3COCl
Original language description
The wavelength control of photochemistry usually results from ultrafast dynamics following the excitation of different electronic states. Here, we investigate the CF3COCl molecule, exhibiting wavelength-dependent photochemistry both via (i) depositing increasing internal energy into a single state and (ii) populating different electronic states. We reveal the mechanism behind the photon-energy dependence by combining nonadiabatic ab initio molecular dynamics techniques with the velocity map imaging experiment. We describe a consecutive mechanism of photodissociation where an immediate release of Cl taking place in an excited electronic state is followed by a slower ground-state dissociation of the CO fragment. The CO release is subject to an activation barrier and is controlled by excess internal energy via the excitation wavelength. Therefore, a selective release of CO along with Cl can be achieved. The mechanism is fully supported by both the measured kinetic energy distributions and anisotropies of the angular distributions. Interestingly, the kinetic energy of the released Cl atom is sensitively modified by accounting for spin-orbit coupling. Given the atmospheric importance of CF3COCl, we discuss the consequences of our findings for atmospheric photochemistry. © 2023 The Authors. Published by American Chemical Society.
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
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA23-07066S" target="_blank" >GA23-07066S: Time-dependent simulations for time-resolved electronic spectroscopies</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
ACS Earth and Space Chemistry
ISSN
2472-3452
e-ISSN
2472-3452
Volume of the periodical
7
Issue of the periodical within the volume
11
Country of publishing house
US - UNITED STATES
Number of pages
12
Pages from-to
2275-2286
UT code for WoS article
001095297500001
EID of the result in the Scopus database
2-s2.0-85177492545