Theoretical Studies of Water Clusters Interacting with Excess Electrons, Protons, and Halide Ions

匹兹堡大学的肯尼斯·乔丹由理论和计算化学计划支持，开展理论研究，研究水团簇与带电粒子，特别是过剩电子、卤离子和质子的相互作用。我们将开发一个用于表征带负电荷的水团簇的灵活的单电子模型势代码，并将其应用于绘制带负电荷的小水团簇的重排路径。此外，还将计算被不同数量的Ar原子“溶剂化”的带负电的水团簇离子的光谱，目的是提供有助于识别实验观测到的离子光谱的信息。在最近的实验的推动下，理论研究将被用来阐明在光激发下碘阴离子-水团簇的重排途径。在第三项研究中，将考察单个质子对水团簇熔化行为的影响，并与最近的实验有关，这些实验表明，水团簇的光致电离产物取决于电荷团簇是类固体还是类液体。这项研究的结果将提供对根本重要的水团簇系统的新见解，以及带电粒子在主体水和界面中的行为。水无处不在，对生物过程至关重要。对水分子团簇的研究可以对散装水中的生物和化学现象以及水与其他介质的界面提供有用的见解。最近对水团簇以及与其他分子、离子和过剩电子相互作用的团簇的实验和理论研究，为这些新物种的结构和其他性质提供了相当大的洞察力。这项研究将解决在活跃的水集群研究领域中提出的新问题的理论方面。

Kenneth Jordan of the University of Pittsburgh is supported by the Theoretical and Computational Chemistry Program to carry out theoretical studies that address the interactions of water clusters with charged particles, in particular, excess electrons, halide ions, and protons. A flexible one-electron model-potential code for characterizing negatively charged water clusters will be developed and applied in mapping out the rearrangement pathways for small negatively charged water clusters. In addition, spectra will be calculated for negatively charged water cluster ions "solvated" by variable numbers of argon atoms, with the goal of providing information useful in identifying experimentally observed ion spectra. Motivated by recent experiments, theoretical studies will be undertaken to elucidate the rearrangement pathways accessible following photoexcitation of iodine anion-water clusters. In a third research thrust, the impact of a single proton on the melting behavior of water clusters will be examined and related to recent experiments that indicate that products from photoionization of water clusters depend on whether the charge clusters are solid-like or liquid-like. The outcomes of this research will provide new insights into the fundamentally important water cluster systems, as well as the behavior of charged particles in bulk water and interfaces. Water is ubiquitous and crucial for biological processes. Studies of clusters of water molecules can provide useful insights into biological and chemical phenomena in bulk water and at water interfaces with other media. Recent experimental and theoretical studies of water clusters, and clusters interacting with other molecules, ions, and excess electrons, have provided considerable insight into the structures and other properties of these novel species. This research will address theoretical aspects of new issues raised in the active area of water cluster research.