How Anion Chaotrope Changes the Local Structure of Water: Insights from Photoelectron Spectroscopy and Theoretical Modeling of SCN‿/sup> Water Clusters

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• 作者：Marat Valiev ; Shihu H. M. Deng ; Xue-Bin Wang
• 刊名：Journal of Physical Chemistry B
• 出版年：2016
• 出版时间：March 3, 2016
• 年：2016
• 卷：120
• 期：8
• 页码：1518-1525
• 全文大小：421K
• ISSN：1520-5207

文摘

The behavior of charged solute molecules in aqueous solutions is often classified using the concept of kosmotropes (“structure makers”) and chaotropes (“structure breakers”). There is a growing consensus that the key to kosmotropic/chaotropic behaviors lies in the local solvent region, but the exact microscopic basis for such differentiation is not well-understood. This issue is examined in this work by analyzing size selective solvation of a well-known chaotrope, a negatively charged SCN^– molecule. Combining experimental photoelectron spectroscopy measurements with theoretical modeling, we examine evolution of solvation structure up to eight waters. We observe that SCN^– indeed fits the description of weakly hydrated ion, and its solvation is heavily driven by stabilization of water–water interaction network. However, the impact on water structure is more subtle than that associated with “structure breaker”. In particular, we observe that the solvation structure of SCN^– preserves the “packing” structure of the water network but changes local directionality of hydrogen bonds in the local solvent region. The resulting effect is closer to that of “structure weakener”, where solute can be readily accommodated into the native water network, at the cost of compromising its stability due to constraints on hydrogen bonding directionality.