To enhance our understanding of the mechanism of water-exchange around aqueous ions, we carried out a systematic study using molecular dynamics simulations with polarizable potential models.  The mechanistic properties associated with the water-exchange process, such as potentials of mean force, time dependent transmission coefficients, and the corresponding rate constants, were examined using transition rate theory, the reactive flux method, and Grote-Hynes treatments of the dynamic response of the solvent.  We compared the computed rate theory results with results from previous corresponding studies in which classical non-polarizable force fields were used. We also studied the effect of pressure on water-exchange rates and the corresponding activation volume.  Our computed rate results for water exchange increase with pressure; therefore, a small negative activation volume is observed. Our future research efforts will focus on understanding the influence of nuclear quantum mechanical effects on the properties of ions in aqueous solution such as the water-exchange rate and the corresponding transmission coefficients using ring polymer MD techniques.

Computational studies of water exchange around aqueous ions with polarizable potential models

248th National Meeting (2014)

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