TY  - INPR
AV  - public
Y1  - 2024/02/19/
TI  - A First Proposal on the Nitrobenzene Photorelease Mechanism of NO2 and Its Relation to NO Formation through a Roaming Mechanism
EP  - 2221
UR  - https://doi.org/10.1021/acs.jpclett.3c03457
ID  - discovery10187533
N2  - 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 n?* 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.
SP  - 2216
N1  - © 2024 The Authors. Published by American Chemical Society. This publication is licensed under  CC-BY 4.0 (https://creativecommons.org/licenses/by/4.0/).
A1  - Giussani, Angelo
A1  - Worth, Graham A
JF  - The Journal of Physical Chemistry Letters
ER  -