On the Wavelength-Dependent Photochemistry of the Atmospheric Molecule CF3COCl

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

On the Wavelength-Dependent Photochemistry of the Atmospheric Molecule CF3COCl

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

On the Wavelength-Dependent Photochemistry of the Atmospheric Molecule CF3COCl

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA23-07066S" target="_blank" >GA23-07066S: Časově závislé simulace pro časově rozlišené elektronové spektroskopie</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

ACS Earth and Space Chemistry

ISSN

2472-3452

e-ISSN

2472-3452

Svazek periodika

7

Číslo periodika v rámci svazku

11

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

2275-2286

Kód UT WoS článku

001095297500001

EID výsledku v databázi Scopus

2-s2.0-85177492545