title: Computational studies of water exchange around aqueous Li+ with polarizable potential models.
abstract: To enhance our understanding of the mechanism of water-exchange around aqueous Li(+), we carried out a systematic study on this system 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. Our computed barrier heights for water exchange are significantly larger than those obtained using classical non-polarizable force fields. 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.
authors.affiliation: Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 93352, USA.
authors.forename: Liem X
authors.initials: LX
authors.lastname: Dang
authors.forename: Harsha V R
authors.initials: HV
authors.lastname: Annapureddy