Energy partitioning and spin-orbit effects in the photodissociation of higher chloroalkanes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F21%3A43922495" target="_blank" >RIV/60461373:22340/21:43922495 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388955:_____/21:00543206 RIV/00216208:11320/21:10431156

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlelanding/2021/cp/d1cp01371h" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2021/cp/d1cp01371h</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d1cp01371h" target="_blank" >10.1039/d1cp01371h</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Energy partitioning and spin-orbit effects in the photodissociation of higher chloroalkanes

Popis výsledku v původním jazyce

We investigate the photodissociation dynamics of the C-Cl bond in chloroalkanes CH3Cl,n-C3H7Cl, i-C3H7Cl,n-C5H11Cl, combining velocity map imaging (VMI) experiment and directab initiodynamical simulations. The Cl fragment kinetic energy distributions (KEDs) from the VMI experiment exhibit a single peak with maximum close to 0.8 eV, irrespective of the alkyl chain length and C-Cl bond position. In contrary to CH3Cl, where less than 10% of the available energy is deposited into the internal excitation of the CH3fragment, for all higher chloroalkanes around 40% to 60% of the available energy goes into the alkyl fragment excitation. We apply the classical hard spheres and spectator model to explain the energy partitioning, and compare the classical approach with directab initiodynamics simulations. The alkyl chain appears to be a soft, energy absorbing unit. We further investigate the role of the spin-orbit effects on the excitation and dynamics. Combining our experimental data with theory allows us to derive the probability of the direct absorption into the triplet electronic state as well as the probabilities for intersystem crossing. The results indicate an increasing direct absorption into the triplet state with increasing alkyl chain length. © the Owner Societies 2021.

Název v anglickém jazyce

Energy partitioning and spin-orbit effects in the photodissociation of higher chloroalkanes

Popis výsledku anglicky

We investigate the photodissociation dynamics of the C-Cl bond in chloroalkanes CH3Cl,n-C3H7Cl, i-C3H7Cl,n-C5H11Cl, combining velocity map imaging (VMI) experiment and directab initiodynamical simulations. The Cl fragment kinetic energy distributions (KEDs) from the VMI experiment exhibit a single peak with maximum close to 0.8 eV, irrespective of the alkyl chain length and C-Cl bond position. In contrary to CH3Cl, where less than 10% of the available energy is deposited into the internal excitation of the CH3fragment, for all higher chloroalkanes around 40% to 60% of the available energy goes into the alkyl fragment excitation. We apply the classical hard spheres and spectator model to explain the energy partitioning, and compare the classical approach with directab initiodynamics simulations. The alkyl chain appears to be a soft, energy absorbing unit. We further investigate the role of the spin-orbit effects on the excitation and dynamics. Combining our experimental data with theory allows us to derive the probability of the direct absorption into the triplet electronic state as well as the probabilities for intersystem crossing. The results indicate an increasing direct absorption into the triplet state with increasing alkyl chain length. © the Owner Societies 2021.

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

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

Rok uplatnění

2021

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

—

Svazek periodika

23

Číslo periodika v rámci svazku

26

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

12

Strana od-do

14340-14351

Kód UT WoS článku

000665758200001

EID výsledku v databázi Scopus

2-s2.0-85109539249