Hydrogen isotope exchange kinetics between H2O and H4SiO4 from ab initio calculations

Hydrogen isotope exchange between water and orthosilicic acid (H4SiO4) was modeled using B3LYP calculations and classical transition-state theory. Configurations of 1, 2, 3 and 7 water molecules and H4SiO4 were used to investigate energetically viable reaction pathways. An upper-bound of 71 kJ/mol was assumed for the zero-point energy corrected barrier (ZPECB) because this is the experimentally determined activation energy for Si-O bond breaking (Rimstidt and Barnes, 1980) and ZPECB is expected to be close to this value. Long range solvation forces were accounted for using the integral equation formalism polarized continuum model (IEFPCM; Cances et al., 1997). Primary and secondary isotope effects were computed by exchanging hydrogen atoms with deuterium. Results show that reaction mechanisms involving 3 and 7 water molecules have ZPECB of 34 to 38 kJ/mol, whereas those involving 1 and 2 water molecules have ZPECB in excess of the set upper-bound. The lower range of ZPECB with 3 or 7 water molecules is reasonable to explain rapid hydrogen isotope exchange with silicates. Rate constant calculations accounting for tunneling, anharmonicity and scaling factors indicate that the reaction is fast and equilibrium can be assumed under most geologic conditions. Copyright (C) 2003 Elsevier Science Ltd.