Photochemistry of HNSO2 in cryogenic matrices: spectroscopic identification of the intermediates and mechanism.
Phys Chem Chem Phys
; 22(15): 7975-7983, 2020 Apr 15.
Article
em En
| MEDLINE
| ID: mdl-32236270
ABSTRACT
Small molecules solely consisting of H, N, O, and S are highly relevant intermediates in atmospheric chemistry and biology. Even though several isomers of [HNO2S] have been computationally predicted, only the IR spectra for the two lowest-energy isomers HNSO2 and syn-syn HONSO have been previously reported. Herein, the photochemistry (193 nm laser) of HNSO2 in N2-, Ne-, and Ar-matrices (≤15 K) has been studied. Aside from syn-syn HONSO, several new isomers including anti-syn HONSO, gauche-syn HOSNO, syn HOS(O)N, anti HOS(O)N, syn HS(O)NO, anti HN(O)SO, gauche-syn HSONO, and an elusive caged-radical pair HOSËËNO have been identified. Additionally, the formation of fragments HONO, HOË, ËNO, and ËNO2 has also been observed. The characterization of these species with matrix-isolation IR and UV/Vis spectroscopy is supported by 15N-labeling and quantum chemical computations at the B3LYP/6-311++G(3df,3pd) level. Furthermore, the photo-induced isomerization reactions, including the conformational conversion of syn-syn HONSO â anti-syn HONSO and reversible isomerization of HOSNO â anti-syn HONSO, syn-syn HONSO â HN(O)SO, HSONO â HS(O)NO, and HOSËËNO â HOSNO have also been observed, and the underlying mechanism is discussed.
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Base de dados:
MEDLINE
Tipo de estudo:
Diagnostic_studies
Idioma:
En
Ano de publicação:
2020
Tipo de documento:
Article