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Photochemistry of HNSO2 in cryogenic matrices: spectroscopic identification of the intermediates and mechanism
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2020/03/26 , DOI: 10.1039/d0cp00962h Changyun Chen 1, 2, 3, 4, 5 , Lina Wang 5, 6, 7, 8 , Xiaofang Zhao 1, 2, 3, 4, 5 , Zhuang Wu 1, 2, 3, 4, 5 , Bastian Bernhardt 9, 10, 11, 12 , André K. Eckhardt 9, 10, 11, 12 , Peter R. Schreiner 9, 10, 11, 12 , Xiaoqing Zeng 1, 2, 3, 4, 5
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2020/03/26 , DOI: 10.1039/d0cp00962h Changyun Chen 1, 2, 3, 4, 5 , Lina Wang 5, 6, 7, 8 , Xiaofang Zhao 1, 2, 3, 4, 5 , Zhuang Wu 1, 2, 3, 4, 5 , Bastian Bernhardt 9, 10, 11, 12 , André K. Eckhardt 9, 10, 11, 12 , Peter R. Schreiner 9, 10, 11, 12 , Xiaoqing Zeng 1, 2, 3, 4, 5
Affiliation
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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 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 syn–syn HONSO → anti–syn HONSO and reversible isomerization of HOSNO ↔ anti–syn HONSO, syn–syn HONSO ↔ HN(O)SO, HSONO ↔ HS(O)NO, and HOS˙⋯˙NO ↔ HOSNO have also been observed, and the underlying mechanism is discussed.
中文翻译：
低温基质中HNSO2的光化学：中间体的光谱鉴定和机理
仅由H，N，O和S组成的小分子是大气化学和生物学中高度相关的中间体。尽管已经通过计算预测了[HNO 2 S]的几种异构体，但以前仅报道了两种最低能量异构体HNSO 2和syn – syn HONSO的红外光谱。在此，研究了在N 2-，Ne-和Ar矩阵（≤15 K）中HNSO 2的光化学（193 nm激光）。除了syn - syn HONSO，还有几种新的异构体，包括anti - syn HONSO，gauche - syn HOSNO，syn已经确定了HOS（O）N，抗HOS（O）N，顺式HS（O）NO，抗HN（O）SO，gauche – syn HSONO以及难以捉摸的笼型自由基对HOS˙⋯˙NO。此外，片段HONO，HO，NO，和NO的形成2也被观察到。通过15 N标记和B3LYP / 6-311 ++ G（3df，3pd）水平的量子化学计算，可以通过基质隔离IR和UV / Vis光谱对这些物质进行表征。此外，光诱导的异构化反应包括syn - syn HONSO→反– syn的构象转化HONSO和HOSNO↔的可逆异构化的抗-顺式HONSO，顺式-顺式HONSO↔HN（O）SO，HSONO↔HS（O）NO，和HOS⋯NO↔HOSNO也已观察到，与底层机制进行了讨论。
更新日期：2020-04-15
中文翻译：
低温基质中HNSO2的光化学：中间体的光谱鉴定和机理
仅由H，N，O和S组成的小分子是大气化学和生物学中高度相关的中间体。尽管已经通过计算预测了[HNO 2 S]的几种异构体，但以前仅报道了两种最低能量异构体HNSO 2和syn – syn HONSO的红外光谱。在此，研究了在N 2-，Ne-和Ar矩阵（≤15 K）中HNSO 2的光化学（193 nm激光）。除了syn - syn HONSO，还有几种新的异构体，包括anti - syn HONSO，gauche - syn HOSNO，syn已经确定了HOS（O）N，抗HOS（O）N，顺式HS（O）NO，抗HN（O）SO，gauche – syn HSONO以及难以捉摸的笼型自由基对HOS˙⋯˙NO。此外，片段HONO，HO，NO，和NO的形成2也被观察到。通过15 N标记和B3LYP / 6-311 ++ G（3df，3pd）水平的量子化学计算，可以通过基质隔离IR和UV / Vis光谱对这些物质进行表征。此外，光诱导的异构化反应包括syn - syn HONSO→反– syn的构象转化HONSO和HOSNO↔的可逆异构化的抗-顺式HONSO，顺式-顺式HONSO↔HN（O）SO，HSONO↔HS（O）NO，和HOS⋯NO↔HOSNO也已观察到，与底层机制进行了讨论。
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