First principles molecular dynamics study of interlayer water and cations in vermiculite

Ikeda, Takashi

To clarify possible origins of irreversible adsorption exhibited by cesium on clay minerals, we performed FPMD simulations for vermiculite including water molecules along with Mg, K, and Cs in its interlayers. Our close examination on the structural and dynamical properties of interlayer water included together with the cations shows that Mg and Cs form respectively outer- and inner-sphere surface complexes in the interlayers, while K forms both types. The structure of electric double layers formed in the interlayers is found to depend significantly on the type of surface complexes of interlayer cations. The reorientational motions of HO are suggested to be enhanced by Cs in contrast to a minor influence of Mg and K. Our observed enhanced diffusion of interlayer HO along with their rapid reorientation indicates that Cs ions work as structure-breaking ions even in confined 2-dimensional interlayers.