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Molecular dynamics calculation of the activation volume for water exchange on Li+
James R Rustad1, Andrew G Stack
1Department of Geology, University of California-Davis, One Shields Avenue, Davis, CA 95616, USA. jrrustad@ucdavis.edu
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.
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