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Photochemistry of HNSO2 in cryogenic matrices: spectroscopic identification of the intermediates and mechanism

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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 synsyn 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 synsyn HONSO, several new isomers including antisyn HONSO, gauchesyn HOSNO, syn HOS(O)N, anti HOS(O)N, syn HS(O)NO, anti HN(O)SO, gauchesyn HSONO, and an elusive caged-radical pair HOS˙⋯˙NO have been identified. Additionally, the formation of fragments HONO, HO˙, ˙NO, and ˙NO2 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 synsyn HONSO → antisyn HONSO and reversible isomerization of HOSNO ↔ antisyn HONSO, synsyn HONSO ↔ HN(O)SO, HSONO ↔ HS(O)NO, and HOS˙⋯˙NO ↔ HOSNO have also been observed, and the underlying mechanism is discussed.

Graphical abstract: Photochemistry of HNSO2 in cryogenic matrices: spectroscopic identification of the intermediates and mechanism

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Article information


Submitted
20 Feb 2020
Accepted
26 Mar 2020
First published
26 Mar 2020

Phys. Chem. Chem. Phys., 2020, Advance Article
Article type
Paper

Photochemistry of HNSO2 in cryogenic matrices: spectroscopic identification of the intermediates and mechanism

C. Chen, L. Wang, X. Zhao, Z. Wu, B. Bernhardt, A. K. Eckhardt, P. R. Schreiner and X. Zeng, Phys. Chem. Chem. Phys., 2020, Advance Article , DOI: 10.1039/D0CP00962H

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