Direct Observation of HOON Intermediate in the Photochemistry of HONO.

Li, Xiaolong; Fan, Wenbin; Wang, Lina; Jiang, Junjie; Du, Yanqi; Fang, Wei; Trabelsi, Tarek; Francisco, Joseph S; Yang, Jiawei; Li, Jun; Zhou, Mingfei; Zeng, Xiaoqing

Li, Xiaolong; Fan, Wenbin; Wang, Lina; Jiang, Junjie; Du, Yanqi; Fang, Wei; Trabelsi, Tarek; Francisco, Joseph S; Yang, Jiawei; Li, Jun; Zhou, Mingfei; Zeng, Xiaoqing.

Afiliação

Li X; Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China.
Fan W; Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China.
Wang L; Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China.
Jiang J; Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China.
Du Y; Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China.
Fang W; Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China.
Trabelsi T; Department of Earth and Environment Science, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6243, United States.
Francisco JS; Department of Earth and Environment Science, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6243, United States.
Yang J; School of Chemistry and Chemical Engineering and Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing 401331, China.
Li J; School of Chemistry and Chemical Engineering and Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing 401331, China.
Zhou M; Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China.
Zeng X; Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China.

J Am Chem Soc ; 146(29): 20494-20499, 2024 Jul 24.

Article em En | MEDLINE | ID: mdl-39001838

ABSTRACT

ABSTRACT

The photochemistry of nitrous acid (HONO), encompassing dissociation into OH and NO as well as the reverse association reaction, plays a pivotal role in atmospheric chemistry. Here, we report the direct observation of nitrosyl-O-hydroxide (HOON) in the photochemistry of HONO, employing matrix-isolation IR and UV-vis spectroscopy. Despite a barrier of approximately 30 kJ/mol, HOON undergoes spontaneous rearrangement to the more stable HONO isomer through quantum mechanical tunneling, with a half-life of 28 min at 4 K. Kinetic isotope effects and instanton theory calculations reveal that the tunneling process involves the concerted motion of the NO moiety (65.2%) and the hydrogen atom (32.3%). Our findings underscore the significance of HOON as a key intermediate in the photolytic dissociation-association cycle of HONO at low temperatures.

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Texto completo: 1 Bases de dados: MEDLINE Idioma: En Revista: J Am Chem Soc Ano de publicação: 2024 Tipo de documento: Article País de afiliação: China