Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstraße 25, 6020Innsbruck, Austria.
Institute of Research Management and Services (IPPP), Research and Innovation Management Complex, University of Malaya, Kuala Lumpur50603, Malaysia.
J Am Soc Mass Spectrom. 2023 Mar 1;34(3):337-354. doi: 10.1021/jasms.2c00290. Epub 2023 Feb 6.
The precise location of an ion or electron, whether it is internally solvated or residing on the surface of a water cluster, remains an intriguing question. Subtle differences in the hydrogen bonding network may lead to a preference for one or the other. Here we discuss spectroscopic probes of the structure of gas-phase hydrated ions in combination with quantum chemistry, as well as H/D exchange as a means of structure elucidation. With the help of nanocalorimetry, we look for thermochemical signatures of surface vs internal solvation. Examples of strongly size-dependent reactivity are reviewed which illustrate the influence of surface vs internal solvation on unimolecular rearrangements of the cluster, as well as on the rate and product distribution of ion-molecule reactions.
离子或电子的确切位置，无论是在溶剂内部还是水簇的表面，都是一个有趣的问题。氢键网络的细微差异可能导致对一种或另一种的偏好。在这里，我们讨论了与量子化学相结合的气态水合离子结构的光谱探针，以及 H/D 交换作为结构阐明的一种手段。借助纳米量热法，我们寻找表面和内部溶剂化的热化学特征。我们回顾了一些强烈依赖于尺寸的反应实例，这些实例说明了表面和内部溶剂化对簇的分子内重排以及离子-分子反应的速率和产物分布的影响。
