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

被引：11

作者：

Algarra, Manuel ^{[1
]}

Soto, Juan ^{[2
]}

Pinto da Silva, Luis ^{[6
,7
]}

Soledad Pino-Gonzalez, M. ^{[8
]}

Enrique Rodriguez-Borges, J. ^{[6
]}

Mascetti, Joelle ^{[9
]}

Borget, Fabien ^{[10
]}

Reisi-Vanani, Adel ^{[11
]}

Luque, Rafael ^{[3
,4
,5
]}

机构：

[1] Univ Madeira, CQM, P-9020105 Funchal, Portugal

[2] Univ Malaga, Fac Sci, Dept Phys Chem, Malaga 29016, Spain

[3] Univ Cordoba, Dept Organ Chem, Cordoba 14014, Spain

[4] Univ Cordoba, Dept Organ Chem, Cbrdoba 14014, Spain

[5] RUDN Univ, Peoples Friendship Univ Russia, Moscow 117198, Russia

[6] Univ Porto, Dept Chem & Biochem, Chem Res Unit CIQUP, Fac Sci, P-4169007 Porto, Portugal

[7] Univ Porto, LACOMEPHI, GreenUP, Dept Geosci Environm & Terr Planning,Fac Sci, P-4169007 Porto, Portugal

[8] Univ Malaga, Fac Sci, Dept Organ Chem, Malaga 29016, Spain

[9] Univ Bordeaux, Inst Sci Mol, F-33405 Talence, France

[10] Aix Marseille Univ, Phys Interact Ion & Mol, F-13007 Marseille, France

[11] Univ Kashan, Fac Chem, Dept Phys Chem, Kashan 8731751167, Iran

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2020年 / 124卷 / 10期

关键词：

MULTICONFIGURATIONAL 2ND-ORDER PERTURBATION; GRAPHICAL USER-INTERFACE; SELF-CONSISTENT-FIELD; THERMAL-DECOMPOSITION; MATRIX-ISOLATION; AB-INITIO; BASIS-SETS; PHOTOCHEMICAL DECOMPOSITION; PHOTOELECTRON-SPECTROSCOPY; COMPUTATIONAL CHEMISTRY;

D O I：

10.1021/acs.jpca.9b11157

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

UV photodecomposition of azidomethyl methyl sulfide (AMMS) yields a transient 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 Moller-Plesset methods.

引用

页码：1911 / 1921

页数：11

共 96 条

[81] Comment on "Multiconfigurational perturbation theory can predict a false ground state" by C. Camacho, R. Cimiraglia and H. A. Witek, Phys. Chem. Chem. Phys., 2010, 12, 5058 [J].