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The femtochemistry of nitrobenzene following excitation at 240 nm

Abstract:
Although the photochemistry of nitrobenzene has been extensively studied, the assignment of fragmentation channels and their specific dynamics remains challenging. Here the photochemistry of nitrobenzene following 240 nm excitation into its S4 excited singlet state is investigated by femtosecond laser-induced ionization using an intense 800 nm pulse, coupled with time-resolved Coulomb explosion imaging and covariance mapping. We assign photochemical channels by observing correlations between the molecular fragment ions of the associated product pairs, enabling the time-resolved dynamics of channels leading to NO, NO2, and C6H5NO to be fully characterized. NO is produced via two distinct pathways, leading to translationally cold and hot photofragments with risetimes of ~ 8 ps and ~ 14 ps, respectively. NO2 photofragments are characterised by a bimodal risetime of ~ 8 ps and ≳ 2 ns, and can be detected within the first picosecond following ultra-violet photon absorption. C6H5NO is formed with a risetime of 17 ps. Kinetic energy disposals determined for the three chemical channels agree well with previous work. The techniques employed offer new opportunities to study the time-resolved photochemistry of relatively complex molecules in the gas phase.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1038/s42004-025-01672-2

Authors

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Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Chemistry Research Laboratory
Role:
Author
ORCID:
0000-0002-4296-7944
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Chemistry Research Laboratory
Role:
Author
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Chemistry Research Laboratory
Role:
Author
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Chemistry Research Laboratory
Role:
Author
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Sub-Department of Physical and Theoretical Chemistry
Role:
Author
ORCID:
0000-0002-7317-8649


More from this funder
Funder identifier:
https://ror.org/0439y7842
Grant:
EP/S028617/1
EP/V026690/1


Publisher:
Springer Nature
Journal:
Communications Chemistry More from this journal
Volume:
8
Issue:
1
Article number:
268
Place of publication:
England
Publication date:
2025-09-01
Acceptance date:
2025-08-21
DOI:
EISSN:
2399-3669
Pmid:
40890491


Language:
English
Keywords:
Pubs id:
2285298
Local pid:
pubs:2285298
Deposit date:
2025-09-12
ARK identifier:

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