Different Dynamics of CH3 and Cl Fragments from Photodissociation of CH3Cl in Clusters

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F20%3A00532538" target="_blank" >RIV/61388955:_____/20:00532538 - isvavai.cz</a>

Alternative codes found

RIV/00216208:11320/20:10422915

Result on the web

<a href="http://hdl.handle.net/11104/0310999" target="_blank" >http://hdl.handle.net/11104/0310999</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.0c05926" target="_blank" >10.1021/acs.jpca.0c05926</a>

Result language

angličtina

Original language name

Different Dynamics of CH3 and Cl Fragments from Photodissociation of CH3Cl in Clusters

Original language description

We investigate the photodissociation of CH3Cl at 193.3 nm using the velocity map imaging technique in (CH3Cl)n clusters in comparison with isolated molecules. Our results for the isolated molecules are in excellent agreement with the previous study of Cl fragments, and we extend it by detecting also the CH3(ν = 0) fragments. For the clusters, the Cl (and Cl*) and CH3 fragment images are dominated by intense central isotropic features. The corresponding kinetic energy distributions (KEDs) reveal significant differences in the CH3 and Cl fragment dynamics. While the CH3 fragments exhibit a very narrow near-zero kinetic energy peak, pointing to almost complete caging of CH3 fragments, the Cl (and Cl*) fragments show more structured KEDs extending all the way to the maximum available kinetic energy. The Cl KED spectra have a bimodal character with two broad peaks close to zero and around 0.6 eV. We observe a higher ICH3(ν=0)/ICl signal ratio from the clusters compared to the monomers. This is attributed to an efficient quenching of the higher vibrationally excited ν2 states of the CH3 fragments generated in the photodissociation. Collisional quenching of these excited states in clusters enhances the detected CH3(ν = 0) state. Finally, we determine the [Cl*]/[Cl] branching ratio for the photodissociation pathways in the clusters as ≈0.55 ± 0.15 compared to 0.86 for the isolated molecules, which is also attributed to the collisional quenching of the excited state in the clusters. The clusters and photofragment dynamics are discussed.

Czech name

—

Czech description

—

Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/GA19-14105S" target="_blank" >GA19-14105S: Heterogeneous reactions of the atmospheric radicals on clusters.</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2020

Confidentiality

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

Name of the periodical

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

—

Volume of the periodical

124

Issue of the periodical within the volume

38

Country of publishing house

US - UNITED STATES

Number of pages

11

Pages from-to

7633-7643

UT code for WoS article

000575821700002

EID of the result in the Scopus database

2-s2.0-85091358281