eprintid: 10187533
rev_number: 7
eprint_status: archive
userid: 699
dir: disk0/10/18/75/33
datestamp: 2024-02-22 11:46:56
lastmod: 2024-02-22 11:46:56
status_changed: 2024-02-22 11:46:56
type: article
metadata_visibility: show
sword_depositor: 699
creators_name: Giussani, Angelo
creators_name: Worth, Graham A
title: A First Proposal on the Nitrobenzene Photorelease Mechanism of NO2 and Its Relation to NO Formation through a Roaming Mechanism
ispublished: inpress
divisions: UCL
divisions: B04
divisions: C06
divisions: F56
note: © 2024 The Authors. Published by American Chemical Society. This publication is licensed under  CC-BY 4.0 (https://creativecommons.org/licenses/by/4.0/).
abstract: Despite the fact that NO2 is considered to be the main photoproduct of nitrobenzene photochemistry, no mechanism has ever been proposed to rationalize its formation. NO photorelease is instead a more studied process, probably due to its application in the drug delivery sector and the study of roaming mechanisms. In this contribution, a photoinduced mechanism accounting for the formation of NO2 in nitrobenzene is theorized based on CASPT2, CASSCF, and DFT electronic structure calculations and CASSCF classical dynamics. A triplet nπ* state is shown to evolve toward C-NO2 dissociation, being, in fact, the only low-lying excited state favoring such a deformation. Along the triplet dissociation path, the possibility to decay to the singlet ground state results in the frustration of the dissociation and in the recombination of the fragments, either back to the nitro or the nitrite isomer. The thermal decomposition of the latter to NO constitutes globally a roaming mechanism of NO formation.
date: 2024-02-19
date_type: published
official_url: https://doi.org/10.1021/acs.jpclett.3c03457
oa_status: green
full_text_type: pub
language: eng
primo: open
primo_central: open_green
verified: verified_manual
elements_id: 2248524
doi: 10.1021/acs.jpclett.3c03457
medium: Print-Electronic
lyricists_name: Worth, Graham
lyricists_id: GWORT12
actors_name: Flynn, Bernadette
actors_id: BFFLY94
actors_role: owner
full_text_status: public
publication: The Journal of Physical Chemistry Letters
pagerange: 2216-2221
event_location: United States
citation:        Giussani, Angelo;    Worth, Graham A;      (2024)    A First Proposal on the Nitrobenzene Photorelease Mechanism of NO2 and Its Relation to NO Formation through a Roaming Mechanism.                   The Journal of Physical Chemistry Letters     pp. 2216-2221.    10.1021/acs.jpclett.3c03457 <https://doi.org/10.1021/acs.jpclett.3c03457>.    (In press).    Green open access   
 
document_url: https://discovery.ucl.ac.uk/id/eprint/10187533/1/giussani-worth-2024-a-first-proposal-on-the-nitrobenzene-photorelease-mechanism-of-no2-and-its-relation-to-no-formation.pdf