Kelleher Patrick J, Menges Fabian S, DePalma Joseph W, Denton Joanna K, Johnson Mark A, Weddle Gary H, Hirshberg Barak, Gerber R Benny
Department of Chemistry, Yale University , New Haven, Connecticut 06525, United States.
Department of Chemistry, Fairfield University , Fairfield, Connecticut 06824, United States.
J Phys Chem Lett. 2017 Oct 5;8(19):4710-4715. doi: 10.1021/acs.jpclett.7b02120. Epub 2017 Sep 18.
The heterogeneous reaction of NO with sea spray aerosols yields the ClNO molecule, which is postulated to occur through water-mediated charge separation into NO and NO ions followed by association with Cl. Here we address an alternative mechanism where the attack by a halide ion can yield XNO by direct insertion in the presence of water. This was accomplished by reacting X(DO) (X = Cl, Br, I) cluster ions with NO to produce ions with stoichiometry [XNO]. These species were cooled in a 20 K ion trap and structurally characterized by vibrational spectroscopy using the D messenger tagging technique. Analysis of the resulting band patterns with DFT calculations indicates that they all correspond to exit channel ion-molecule complexes based on the association of NO with XNO, with the NO constituent increasingly perturbed in the order I > Br > Cl. These results establish that XNO can be generated even when more exoergic reaction pathways involving hydrolysis are available and demonstrate the role of the intermediate [XNO] in the formation of XNO.
一氧化氮（NO）与海喷雾气溶胶的非均相反应产生ClNO分子，据推测该反应是通过水介导的电荷分离成NO⁺和NO⁻离子，随后与Cl结合而发生的。在这里，我们提出了一种替代机制，即卤离子的攻击可以在有水存在的情况下通过直接插入产生XNO。这是通过使X(DO)（X = Cl、Br、I）团簇离子与NO反应来生成化学计量比为[XNO]的离子来实现的。这些物种在20 K离子阱中冷却，并使用D信使标记技术通过振动光谱对其结构进行表征。用密度泛函理论（DFT）计算对所得能带模式的分析表明，它们都对应于基于NO与XNO缔合的出射通道离子 - 分子络合物，其中NO成分按I > Br > Cl的顺序受到越来越大的扰动。这些结果表明，即使存在涉及水解的更多放热反应途径，也可以生成XNO，并证明了中间体[XNO]在XNO形成中的作用。
