Free energies of absorption of alkali ions onto beidellite and montmorillonite surfaces from constrained molecular dynamics simulations

Ab initio Molecular dynamics have been performed to study the free energy of adsorption of alkali atoms onto smectite clay surfaces and to identify the most favourable region in the interlayer for the cations. This is achieved by potential of mean force calculations using a constraint method to determine the lowest free energy configurations of lithium, potassium and sodium beidellite and sodium montmorillonite clays with a monolayer and bilayer of water present in the interlayer region. The constraint method has allowed us to examine the changes in the lowest free energy configuration for each ion with increasing hydration. From this, we can interpret the likelihood of clay swelling from the monolayer to bilayer coverage and compare with experimental observations. We find, that with a bilayer of water present, both lithium beidellite and sodium montmorillonite have their free energy minimum in the centre of the interlayer. For monolayer coverage, the free energy minimum for lithium, sodium and potassium beidellite is approximately the mid-point of the interlayer. Na-beidellite has a lowest free energy region at 6.1 angstrom from the centre of the clay layer for both mono- and bi-layer coverage, while for the potassium counter-ion, commonly used as swelling inhibitor, the free energy profile for K-beidellite shows peaks close to both surfaces at approximately 6.2 and 8.6 angstrom. We find that for systems where the free energy minimum remains in the middle of the interlayer when the hydration levels increase from monolayer to bilayer, it is known experimentally that these systems will swell in contact with water. The move to the middle of the interlayer with increasing hydration is associated with the full hydration sphere of the ion being composed purely of water oxygen atoms, and no clay surface oxygen atoms. (C) 2012 Elsevier Ltd. All rights reserved.