Structure and Dynamics of OH-(aq)
- 1 February 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in Accounts of Chemical Research
- Vol. 39 (2), 151-158
- https://doi.org/10.1021/ar040207n
Abstract
Topological defects in aqueous solution in the form of H(+)(aq) and OH(-)(aq) ions undergo anomalously fast transport via the structural Grotthuss diffusion mechanism. However, while the microscopic details of this process are well understood for H(+)(aq), the corresponding picture for OH(-)(aq) remains unresolved. Mechanistic scenarios proposed previously are critically reviewed with the help of the presolvation concept, which provides a unifying framework for understanding charge migration mechanisms in hydrogen-bonded networks. It is argued that OH(-)(aq) features a nonclassical, in the Lewis sense, hypercoordinated solvation structure. The resulting mechanism deviates substantially from the traditional "mirror image" picture. Within the presolvation concept, it can also be suggested why alternative scenarios are inconsistent with experimental data.Keywords
This publication has 28 references indexed in Scilit:
- The computer simulation of proton transport in waterThe Journal of Chemical Physics, 1999
- Proton Solvation and Proton MobilityIsrael Journal of Chemistry, 1999
- Multistate Empirical Valence Bond Model for Proton Transport in WaterThe Journal of Physical Chemistry B, 1998
- Molecular Mechanism of HCl Acid Ionization in Water: Ab Initio Potential Energy Surfaces and Monte Carlo SimulationsThe Journal of Physical Chemistry B, 1997
- The quantum dynamics of an excess proton in waterThe Journal of Chemical Physics, 1996
- The Grotthuss mechanismChemical Physics Letters, 1995
- Ab initio molecular dynamics simulation of the solvation and transport of hydronium and hydroxyl ions in waterThe Journal of Chemical Physics, 1995
- Ab Initio Molecular Dynamics Simulation of the Solvation and Transport of H3O+ and OH- Ions in WaterThe Journal of Physical Chemistry, 1995
- Proton Transfer, Acid‐Base Catalysis, and Enzymatic Hydrolysis. Part I: ELEMENTARY PROCESSESAngewandte Chemie, 1964
- Proton Conductance and the Existence of the H3O· IonThe Journal of Chemical Physics, 1956