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On the photorelease of nitric oxide by nitrobenzene derivatives; a CASPT2//CASSCF model

Giussani, Angelo; Worth, Graham; (2022) On the photorelease of nitric oxide by nitrobenzene derivatives; a CASPT2//CASSCF model. The Journal of Chemical Physics , 157 (20) , Article 204301. 10.1063/5.0125460. Green open access

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Abstract

Nitroaromatics compounds can photorelease NO after UV absorption. The efficiency of the photoreaction depends on the molecular structure and two features have been pointed out as particularly important for the yield of the process: the presence of methyl groups at the ortho position with respect to the nitro group and the degree of conjugation of the molecule. In the present contribution we provide a theoretical characterization at the CASPT2//CASSCF level of theory of the photorelease of NO for four molecules derived from nitrobenzene through the addition of ortho methyl groups and/or the elongation of the conjugation. Our previously described mechanism obtained for the photorelease of NO in nitrobenzene has been adopted as a model for the process. According to this model, the process proceeds through a reactive singlet-triplet crossing (STC) region that the system can reach from the triplet 3 (π O π*) minimum. The energy barrier that must be surmounted in order to populate the reactive STC can be associated with the efficiency of the photoreaction. The here obtained results display clear differences for the efficiency of the photoreaction in the studied systems, and can be correlated with experimental results. The model thus proves its ability to highlight differences in the photoreaction efficiency for the nitroaromatic compounds studied here.

Type: Article
Title: On the photorelease of nitric oxide by nitrobenzene derivatives; a CASPT2//CASSCF model
Open access status: An open access version is available from UCL Discovery
DOI: 10.1063/5.0125460
Publisher version: https://doi.org/10.1063/5.0125460
Language: English
Additional information: This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions.
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/10159701
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