Application of localized reactivity index in combination with periodic DFT calculation to rationalize the swelling mechanism of clay type inorganic material

Clays are layered alumino-silicates. Clays swell and expand in aqueous solution. This property governs the usage of these materials in synthesis of nano-composites and is a source of many of its catalytic applications. We used both localized and periodic calculations within the realm of density functional theory (DFT) on a series of monovalent (Li+, Na+, K+, Rb+, Cs+), and divalent (Mg2+, Ca2+, Sr2+, Ba2+) cations, to monitor their effect on the swelling of clays. The activity order obtained for the exchangeable cations among all the monovalent and divalent series studied is: Mg2+ > Ca2+ > Sr2+ > Ba2+ > Cs+ > Rb+ > Na+ > Li+ > K+. We have studied two types of clays, montmorillonite and beidellite, with different surface structures and with/without water using periodic calculations. We have calculated the layer spacing at the first, second and third hydration shells of exchangeable cation, to compare with the experimental d-spacing values to correlate with humidity. A novel quantitative scale is proposed in terms of the intermolecular relative nucleophilicity of the active cation sites in their hydrated state through Fukui functions using hard–soft acid base (HSAB) principle. Finally, a swelling mechanism is proposed. This is a unique study where a combination of periodic and localized calculations has been performed to validate the capability of reactivity index calculations in material designing.