Electron-triggered processes in halogenated carboxylates: Dissociation pathways in CF3COCl and its clusters

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F24%3A00581754" target="_blank" >RIV/61388955:_____/24:00581754 - isvavai.cz</a>

Výsledek na webu

<a href="https://hdl.handle.net/11104/0349909" target="_blank" >https://hdl.handle.net/11104/0349909</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/D3CP05387C" target="_blank" >10.1039/D3CP05387C</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Electron-triggered processes in halogenated carboxylates: Dissociation pathways in CF3COCl and its clusters

Popis výsledku v původním jazyce

Trifluoroacetyl chloride, CF3COCl, is produced in the Earth’s atmosphere by photooxidative degradation of hydrochlorofluorocarbons, and represents a potential source of highly reactive halogen radicals. Despite considerable insight obtained into photochemistry of CF3COCl, its reactivity towards electrons has not been addressed so far. We investigate the electron ionization and attachment in isolated CF3COCl molecules and (CF3COCl)N , max. N ≥ 10, clusters using a molecular beam experiment combined with quantum chemical calculations. The ionization of the molecule at 70 eV electron energy leads to a strong fragmentation: weakening of C–C bond yields the CF3+ and COCl+ ions, while the fission of C–Cl bond produces the major CF3CO+ fragment ion. The cluster spectra are dominated by Mn·COCl+ and Mn·CF3CO+ ions (M = CF3COCl). The electron attachment at energies between 1.5–11 eV also leads to the dissociation of the molecule breaking either C–Cl bond at low energies below 3 eV yielding mainly Cl− ion, or dissociating the C–C bond at higher energies above 4 eV leading mainly to CF3− ion. In the clusters, the intact M− n ions are stabilized after the electron attachment at low energies with a contribution of Mn·Cl− fragment ions. At the higher energies, the Mn·Cl− fragments dominate the spectra, and C–C bond dissociation occurs as well yielding Mn·CF3− . Interestingly, Mn·Cl2− ions appear in the spectra at higher energies. We briefly discuss possible atmospheric implications.n

Název v anglickém jazyce

Electron-triggered processes in halogenated carboxylates: Dissociation pathways in CF3COCl and its clusters

Popis výsledku anglicky

Trifluoroacetyl chloride, CF3COCl, is produced in the Earth’s atmosphere by photooxidative degradation of hydrochlorofluorocarbons, and represents a potential source of highly reactive halogen radicals. Despite considerable insight obtained into photochemistry of CF3COCl, its reactivity towards electrons has not been addressed so far. We investigate the electron ionization and attachment in isolated CF3COCl molecules and (CF3COCl)N , max. N ≥ 10, clusters using a molecular beam experiment combined with quantum chemical calculations. The ionization of the molecule at 70 eV electron energy leads to a strong fragmentation: weakening of C–C bond yields the CF3+ and COCl+ ions, while the fission of C–Cl bond produces the major CF3CO+ fragment ion. The cluster spectra are dominated by Mn·COCl+ and Mn·CF3CO+ ions (M = CF3COCl). The electron attachment at energies between 1.5–11 eV also leads to the dissociation of the molecule breaking either C–Cl bond at low energies below 3 eV yielding mainly Cl− ion, or dissociating the C–C bond at higher energies above 4 eV leading mainly to CF3− ion. In the clusters, the intact M− n ions are stabilized after the electron attachment at low energies with a contribution of Mn·Cl− fragment ions. At the higher energies, the Mn·Cl− fragments dominate the spectra, and C–C bond dissociation occurs as well yielding Mn·CF3− . Interestingly, Mn·Cl2− ions appear in the spectra at higher energies. We briefly discuss possible atmospheric implications.n

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

1463-9084

Svazek periodika

26

Číslo periodika v rámci svazku

6

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

9

Strana od-do

5640-5648

Kód UT WoS článku

001153945000001

EID výsledku v databázi Scopus

2-s2.0-85184060846