The Competition between Hydrogen, Halogen, and Covalent Bonding in Atmospherically Relevant Ammonium Iodate Clusters
The Competition between Hydrogen, Halogen, and Covalent Bonding in Atmospherically Relevant Ammonium Iodate Clusters
复制标题
大气相关碘酸铵簇中氢、卤素和共价键之间的竞争
DOI：
10.1021/jacs.2c10841
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发表时间：
2023
影响因子：
15
通讯作者：
Johnson, Christopher J.
中科院分区：
文献类型：
--
作者：
Frederiks, Nicoline C.;Heaney, Danika D.;Kreinbihl, John J.;Johnson, Christopher J.
含碘团簇有望成为极地和中纬度沿海地区新粒子形成（NPF）事件的中心。在新形成的簇中观察到碘氧化酸和碘氧化物，在污染较严重的中纬度环境中，理论研究表明氨可能会增加生长速度。通过红外光谱和量子化学计算获得了一系列含有氨、碘和五氧化二碘的簇的结构信息。鉴定了质谱中5个最小阳离子簇的结构，发现其中4个结构优先形成卤素和/或共价键，而不是氢键。氨在质子从碘酸组分转移的过程中起着重要的作用，也为模板形成卤素和共价键主链提供了一个支架。对所研究的两个最大的团簇进行的计算表明，团簇内形成了共价i3阴离子。
Iodine-containing clusters are expected to be central to new particle formation (NPF) events in polar and midlatitude coastal regions. Iodine oxoacids and iodine oxides are observed in newly formed clusters, and in more polluted midlatitude settings, theoretical studies suggest ammonia may increase growth rates. Structural information was obtained via infrared (IR) spectroscopy and quantum chemical calculations for a series of clusters containing ammonia, iodic acid, and iodine pentoxide. Structures for five of the smallest cationic clusters present in the mass spectrum were identified, and four of the structures were found to preferentially form halogen and/or covalent bonds over hydrogen bonds. Ammonia is important in proton transfer from iodic acid components and also provides a scaffold to template the formation of a halogen and covalent bonded backbone. The calculations executed for the two largest clusters studied suggested the formation of a covalent I3anion within the clusters.