Water Exchange Rates and Molecular Mechanism around Aqueous Halide Ions

Molecular dynamics simulations were performed to systematically study the water-exchange mechanism around aqueous chloride, bromide, and iodide ions. Transition state theory, Grote–Hynes theory, and the reactive flux method were employed to compute water exchange rates. We computed the pressure depe...

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Published inThe journal of physical chemistry. B Vol. 118; no. 28; pp. 7886 - 7891
Main Authors Annapureddy, Harsha V. R, Dang, Liem X
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 17.07.2014
Subjects
Activation
Anions
Chlorides
Exchange
Flux
Halogens - chemistry
Ion exchangers
Molecular dynamics
Molecular Dynamics Simulation
Pressure
Rate constants
Water - chemistry
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Summary:Molecular dynamics simulations were performed to systematically study the water-exchange mechanism around aqueous chloride, bromide, and iodide ions. Transition state theory, Grote–Hynes theory, and the reactive flux method were employed to compute water exchange rates. We computed the pressure dependence of rate constants and the corresponding activation volumes to investigate the mechanism of the solvent exchange event. The activation volumes obtained using the transition state theory rate constants are negative for all the three anions, thus indicating an associative mechanism. Contrary to the transition state theory results, activation volumes obtained using rate constants from Grote–Hynes theory and the reactive flux method are positive, thus indicating a dissociative mechanism.
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ISSN:1520-6106
1520-5207
DOI:10.1021/jp500402j