Xiaolong Li, Wenbin Fan, Lina Wang, Junjie Jiang, Yanqi Du, Wei Fang, Tarek Trabelsi, Joseph S Francisco, Jiawei Yang, Jun Li, Mingfei Zhou, Xiaoqing Zeng
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引用次数: 0
摘要
亚硝酸（HONO）的光化学反应包括解离成 OH 和 NO 以及反向缔合反应，在大气化学中起着举足轻重的作用。在此，我们利用矩阵隔离红外和紫外-可见光谱技术，报告了在 HONO 的光化学过程中对亚硝基-O-氢氧化物（HOON）的直接观察。尽管存在约 30 kJ/mol 的障碍，HOON 仍能通过量子力学隧道作用自发重排为更稳定的 HONO 异构体，在 4 K 温度下的半衰期为 28 分钟。动力学同位素效应和瞬子理论计算显示，隧穿过程涉及 NO 分子（65.2%）和氢原子（32.3%）的协同运动。我们的发现强调了 HOON 作为 HONO 在低温下光解-解离循环的关键中间体的重要性。
Direct Observation of HOON Intermediate in the Photochemistry of HONO.
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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