Structural Progression in Clusters of Ionized Water, (H2O)n=1-5+
Structural Progression in Clusters of Ionized Water, (H2O)n=1-5+
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DOI：
10.1021/jp509698y
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发表时间：
2015-01-29
影响因子：
2.9
通讯作者：
Steele, Ryan P.
中科院分区：
文献类型：
--
作者：
Herr, Jonathan D.;Talbot, Justin;Steele, Ryan P.
离子水团簇作为水分裂化学的模型，用于能量目的，以及凝聚相系统中的辐射后事件。用运动方程耦合团簇理论方法，给出了氧化水团簇(H2O)(n=1-5)(+)的结构、性质和相对能量。在较小的团簇中，离子-自由基接触对OH中心点H3O+在电离时形成。然而，发现团簇中从n=4到n=5的分子的跃迁划分了离子和自由基分离的倾向的大小区域。这一趋势与最近的实验振动分析是一致的。团簇能量学的分解表明，水对离子的优先溶剂化是这种对分离的主要驱动力，这种分离应该持续到更大的团簇和整体水电离。
Ionized water clusters serve as a model of water-splitting chemistry for energetic purposes, as well as postradiolytic events in condensed-phase systems. Structures, properties, and relative energies are presented for oxidized water clusters, (H2O)(n=1-5)(+), using equation-of-motion coupled-cluster theory approaches. In small clusters, an ion-radical contact pair OH center dot center dot center dot H3O+ is known to form upon ionization. The transition from n = 4 to n = 5 molecules in the cluster, however, is found to demarcate a size regime in which a propensity for the ion and radical to separate exists. This trend is consistent with recent experimental vibrational analyses. Decomposition of the cluster energetics reveals that preferential solvation of the hydronium cation by water serves as the dominant driving force for this pair separation, which should persist in larger clusters and bulk water ionization.