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Different ionization energies were obtained using density functional theory calculations to assign UV-PES spectra. The complete active space self-consistent field and multistate second-order perturbation methods were used to predict the formation of different species present in the thermal decomposition process. N2 and S-methyl-N-sulfenylethanimine are generated at 773\u00a0K. The first step of the reaction is the dissociation of the molecule into nitrene and nitrogen. The spin state (singlet or triplet) of nitrene formed in the first step of the reaction is temperature-dependent. At low temperatures (T \u2264 650\u00a0K), both states are formed with almost the same probability; in contrast, at high temperatures (T \u2265 1000\u00a0K), singlet nitrene is the majority intermediate. From this singlet nitrene, three stable reaction products were detected in the experiments: an imine derivative, a four-member cyclic derivative, and a sulfenyl derivative.<\/jats:p>","DOI":"10.1063\/5.0261967","type":"journal-article","created":{"date-parts":[[2025,5,16]],"date-time":"2025-05-16T10:50:14Z","timestamp":1747392614000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":1,"title":["UV-photoelectron spectroscopy and MS-CASPT2\/CASSCF study of the thermolysis of azidoethyl-methyl sulfide: Characterization and mechanism of the formation of <i>S-<\/i>methy<i>l-N-<\/i>sulfenylethanimine"],"prefix":"10.1063","volume":"162","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2410-8430","authenticated-orcid":false,"given":"Manuel","family":"Algarra","sequence":"first","affiliation":[{"name":"Department of Science, 1 , 31006 Pamplona,","place":["Spain"]},{"name":"INAMAT2-Institute for Advanced Materials and Mathematics, Campus de Arrosadia 1 , 31006 Pamplona,","place":["Spain"]}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8226-4058","authenticated-orcid":false,"given":"Stephane","family":"Labat","sequence":"additional","affiliation":[{"name":"Universit\u00e9 de Pau et des Pays de l\u2019Adour, CNRS, IPREM, Technopole Helioparc-2 2 , Av. 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