Insights into the Photodecomposition of Azidomethyl Methyl Sulfide: A S2/S1 Conical Intersection on Nitrene Potential Energy Surfaces Leading to the Formation of S-Methyl-N-sulfenylmethanimine | Zendy

Manuel Algarra | Zendy; Juan Soto | Zendy; Luís Pinto da Silva | Zendy; M. Soledad Pino-González | Zendy; José E. RodríguezBorges | Zendy; Joëlle Mascetti | Zendy; Fabien Borget | Zendy; Adel ReisiVanani | Zendy; Rafael Luque | Zendy

Open Access

Insights into the Photodecomposition of Azidomethyl Methyl Sulfide: A S₂/S₁ Conical Intersection on Nitrene Potential Energy Surfaces Leading to the Formation of S-Methyl-N-sulfenylmethanimine

Author(s) -

Manuel Algarra,

Juan Soto,

Luís Pinto da Silva,

M. Soledad Pino-González,

José E. RodríguezBorges,

Joëlle Mascetti,

Fabien Borget,

Adel ReisiVanani,

Rafael Luque

Publication year - 2020

Publication title -

the journal of physical chemistry a

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.756

H-Index - 235

eISSN - 1520-5215

pISSN - 1089-5639

DOI - 10.1021/acs.jpca.9b11157

Subject(s) - conical intersection , nitrene , complete active space , singlet state , matrix isolation , sulfide , chemistry , photochemistry , spectroscopy , photodissociation , infrared spectroscopy , perturbation theory (quantum mechanics) , potential energy , computational chemistry , density functional theory , atomic physics , excited state , physics , quantum mechanics , organic chemistry , basis set , catalysis

UV photodecomposition of azidomethyl methyl sulfide (AMMS) yields a transien S -methylthiaziridine which rapidly evolves to S -methyl- N -sulfenylmethanimine at 10 K. This species was detected by infrared matrix isolation spectroscopy. The mechanism of the photoreaction of AMMS has been investigated by a combined approach, using low-temperature matrix isolation FTIR spectroscopy in conjunction with two theoretical methods, namely, complete active space self-consistent field and multiconfigurational second-order perturbation. The key step of the reaction is governed by a S 2 /S 1 conical intersection localized in the neighborhood of the singlet nitrene minimum which is formed in the first reaction step of the photolysis, that is, N 2 elimination from AMMS. Full assignment of the observed infrared spectra of AMMS has been carried out based on comparison with density functional theory and second-order perturbation Møller-Plesset methods.

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