Zhutian Ding and Annabella Selloni, J. Phys. Chem. C 2020, 124, 49, 26741–26747 (2020)
Electrons and ions at metal oxide-water interfaces have a critical role in many phenomena and applications, thus making their properties of considerable interest. We here investigate the behavior of a lithium impurity at the water interface with Li-doped SiO2 using hybrid density functional based ab initio molecular dynamics simulations. We find that the excess electron donated by the lithium dopant localizes on a surface silicon atom and is partially solvated at the aqueous interface. While the position of the excess electron does not change during our ∼60 ps simulation, the lithium cation diffuses from its initial position in the SiO2 subsurface toward the interface and eventually leaches out of the oxide surface and becomes solvated by four water molecules, forming an aqueous Li+-electron complex at the interface. The degree of interaction between the localized electron and the lithium ion controls not only the energy level of the excess electron but also the extent of structural distortion and hydrogen-bonding at the interface. The results of our study can be relevant for understanding the initial stages of glass corrosion, where alkali ions are leached from the surface region by interactions with water.