1. An MS-CASPT2 study of the photodecomposition of 4-methoxyphenyl azide: role of internal conversion and intersystem crossing
- Author
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Juan F. Arenas, Isabel López-Tocón, Juan C. Otero, Francisco J. Avila, Juan Soto, and Daniel Aranda
- Subjects
Nitrene ,Arilazidas ,Photodissociation ,General Physics and Astronomy ,02 engineering and technology ,Conical intersection ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Resonance (chemistry) ,Internal conversion (chemistry) ,Photochemistry ,01 natural sciences ,0104 chemical sciences ,chemistry.chemical_compound ,Intersystem crossing ,chemistry ,Fotoquímica ,Azide ,Resonancia Raman ,Physical and Theoretical Chemistry ,Perturbation theory ,0210 nano-technology - Abstract
Aryl azides photochemistry is strongly dependent on the substituent relative position, as has been studied by time resolved resonant Raman (TR3) spectroscopy for 4-methoxyphenyl azide and its isomer 3-methoxyphenyl azide. When irradiated at 266 nm, the former results in 4,4’-dimethoxyazobenzene whereas the latter forms 1,2-didehydroazepine. It is proposed that the key step of the reactions is the formation of a nitrene derivative. Recently, it has been proposed by us that nitrenes might have a relevant role in the Surface-Enhanced Raman Scattering (SERS) of p-aminothiophenol, however, the molecular mechanism is not well known in neither of these cases. Therefore, we studied the photodecomposition of 4-methoxyphenyl azide using multiconfigurational self-consistent field methods (MC-SCF) with the CAS-SCF and MS-CASPT2 approximations and calculated the resonant Raman spectra of the relevant species using a multi-state version of Albrecht’s vibronic theory. The results propose that the reaction follows a two steps sequence after irradiation at 266 nm: an intersystem crossing 21A’/23A’’ which decays through a 21A’/21A’’ conical intersection producing molecular nitrogen and triplet 4-methoxyphenyl nitrene in its ground state. Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech.
- Published
- 2018