Why direct or reversed Hofmeister series? Interplay of hydration, non-electrostatic potentials, and ion size.
Why direct or reversed Hofmeister series? Interplay of hydration, non-electrostatic potentials, and ion size.
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DOI：
10.1021/la903061h
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发表时间：
2010-03
期刊：
影响因子：
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通讯作者：
D. Parsons;M. Boström;T. Maceina;A. Salis;B. Ninham
中科院分区：
文献类型：
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作者：
D. Parsons;M. Boström;T. Maceina;A. Salis;B. Ninham
本文用改进的Poisson-Boltzmann分析法研究了氯化物电解质中两个氧化硅表面和两个氧化铝表面之间的双电层相互作用。该分析采用了非静电离子表面分散相互作用的基础上从头算离子过剩极化率与有限的离子尺寸。介绍了一种适用于亲液离子紧密水化壳层的水化模型。在SiO2表面发现了正Hofmeister系列（K > Na > Li），而在Al 2 O3表面发现了反Hofmeister系列（Li > Na > K），首次使理论与实验相一致。与未水合离子的计算也表明，表面诱导的脱水可能发生在氧化铝表面。
A modified Poisson-Boltzmann analysis is made of the double layer interaction between two silica surfaces and two alumina surfaces in chloride electrolyte. The analysis incorporates nonelectrostatic ion-surface dispersion interactions based on ab initio ionic excess polarizabilities with finite ion sizes. A hydration model for the tightly held hydration shell of kosmotropic ions is introduced. A direct Hofmeister series (K > Na > Li) is found at the silica surface while the reversed series (Li > Na > K) is found at alumina, bringing theory in line with experiment for the first time. Calculations with unhydrated ions also suggest that surface-induced dehydration may be occurring at the alumina surface.