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