UV-Induced Reaction Pathways in Bromoform Probed with Ultrafast Electron Diffraction.
J Am Chem Soc
; 2024 Oct 07.
Article
in En
| MEDLINE
| ID: mdl-39374484
ABSTRACT
For many chemical reactions, it remains notoriously difficult to predict and experimentally determine the rates and branching ratios between different reaction channels. This is particularly the case for reactions involving short-lived intermediates, whose observation requires ultrafast methods. The UV photochemistry of bromoform (CHBr3) is among the most intensely studied photoreactions. Yet, a detailed understanding of the chemical pathways leading to the production of atomic Br and molecular Br2 fragments has proven challenging. In particular, the role of isomerization and/or roaming and their competition with direct C-Br bond scission has been a matter of continued debate. Here, gas-phase ultrafast megaelectronvolt electron diffraction (MeV-UED) is used to directly study structural dynamics in bromoform after single 267 nm photon excitation with femtosecond temporal resolution. The results show unambiguously that isomerization contributes significantly to the early stages of the UV photochemistry of bromoform. In addition to direct C-Br bond breaking within <200 fs, formation of iso-CHBr3 (Br-CH-Br-Br) is observed on the same time scale and with an isomer lifetime of >1.1 ps. The branching ratio between direct dissociation and isomerization is determined to be 0.4 ± 0.20.6 ± 0.2, i.e., approximately 60% of molecules undergo isomerization within the first few hundred femtoseconds after UV excitation. The structure and time of formation of iso-CHBr3 compare favorably with the results of an ab initio molecular dynamics simulation. The lifetime and interatomic distances of the isomer are consistent with the involvement of a roaming reaction mechanism.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
J Am Chem Soc
/
Journal of the american chemical society
/
J. am. chem. soc
Year:
2024
Document type:
Article
Affiliation country:
United States
Country of publication:
United States