Aqueous Basic Solutions: Hydroxide Solvation, Structural Diffusion, and Comparison to the Hydrated Proton

被引:410
作者
Marx, Dominik [3 ]
Chandra, Amalendu [4 ]
Tuckerman, Mark E. [1 ,2 ]
机构
[1] NYU, Dept Chem, New York, NY 10003 USA
[2] NYU, Courant Inst Math Sci, New York, NY 10003 USA
[3] Ruhr Univ Bochum, Lehrstuhl Theoret Chem, D-44780 Bochum, Germany
[4] Indian Inst Technol, Dept Chem, Kanpur 208016, Uttar Pradesh, India
关键词
INITIO MOLECULAR-DYNAMICS; DENSITY-FUNCTIONAL THEORY; HYDROGEN-BOND DYNAMICS; GENERALIZED GRADIENT APPROXIMATION; ION-WATER CLUSTERS; PROTOTROPIC CHARGE MIGRATION; 1ST PRINCIPLES SIMULATIONS; NUCLEAR-MAGNETIC-RESONANCE; ANION-EXCHANGE MEMBRANES; HCL ACID IONIZATION;
D O I
10.1021/cr900233f
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A scientific review informed about the anomalous diffusion of hydroxide in basic solutions OH-. The discussion was initiated with a review of structural diffusion of H+ in acidic solutions, enabling a comparison to be made. The presentation was based on the formal and unifying 'presolvation concept' that was explained within the context of the H+ diffusion process. A theoretical formalism was used by the researchers to connect the qualitative predictions of the presolvation concept to actual mechanisms and the resulting kinetics in quantitative detail. The theoretical formalism allowed structural diffusion to be analyzed on the basis of appropriately defined population correlation functions. This theoretical framework led to consistent sets of various lifetimes and rates for OH- that were directly compared to H+.
引用
收藏
页码:2174 / 2216
页数:43
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