Asymmetric Hybridization Orbitals at the Charged Interface Initiates New Surface Reactions: A Quantum Mechanics Exploration

Although the first report of Hofmeister effects is over 130 years old, the origins of Hofmeister series remain debated. In this study, quantum mechanics (QM) analyses, dispersion-corrected p-DFT calculations and dynamic light scattering (DLS) determinations are combined with aim to unravel such scientific basis. QM analyses show that, asymmetric hybridization occurs for the outer-shell nsnpz orbitals at charged interfaces, and the asymmetric spz hybridization further initiates two unique processes for the interfacial ions: unusual polarization with a greatly enlarged polarizability and a new type covalent bonding of surface reactions with the asymmetric spz hybridization. The asymmetric hybridization theory is then applied and verified by surface reactions of K+ and Na+ with the charged montmorillonite surface. As predicted by QM analyses, p-DFT calculations show that, under no or low electric fields, the covalent bonding does not exist for both Na+ and K+, while under strong electric fields, the covalent...