title: Molecular dynamics calculation of the activation volume for water exchange on Li+.
abstract: The activation volume of water exchange around Li+ (aq) was determined from reactive flux calculations using molecular dynamics simulations with a classical force field. The barrier height for exchange decreases with pressure, giving a negative activation volume, in agreement with the current paradigm for inferring exchange mechanism from activation volume. However, it is also demonstrated that pressure-dependent transmission effects make a significant contribution to the overall activation volume. These calculations indicate that small activation volumes should not be regarded as mechanistically indicative because of the potential contributions from transmission effects.
authors.affiliation: Department of Geology, University of California-Davis, One Shields Avenue, Davis, CA 95616, USA. jrrustad@ucdavis.edu
authors.forename: James R
authors.initials: JR
authors.lastname: Rustad
authors.forename: Andrew G
authors.initials: AG
authors.lastname: Stack