Modeling water exchange on an aluminum polyoxocation

For the first time, water exchange on a polymeric complex has been modeled using a combination of gas-phase ab initio calculations and molecular dynamics (MD) simulations. The GaO₄Al₁₂(OH)₂₄(H ₂O)₁₂⁷⁺(aq) ion (GaAl₁₂) was chosen because high-quality experimental data exist, including an activation enthalpy (+63 ± 7 kJ/mol) and an activation volume (+3 ± 1 cm ³/mol). We took a two-step approach. First, the local solvent structure and the initial states for reaction were inferred from the molecular dynamics simulations. Second, we used this information to evaluate initial-state structures in the ab initio calculations. The energy differences between the initial and transition states from the ab initio calculations varied from +59 kJ/mol to +53 kJ/mol depending upon details, closely approximating the activation enthalpy.