Water adsorption on olivine(010) surfaces: Effect of alkali and transition metal cation doping.

Dopants have the potential to locally modify water-olivine interactions, which can impact geological processes, such as weathering, CO2 sequestration, and abiotic hydrocarbon generation. As a first step in understanding the role of dopants on the water structure and chemistry at water-olivine interfaces, water monomer adsorption on alkaline earth (AE) and transition metal (TM) doped forsterite(010) [Mg2SiO4(010)] surfaces was studied using density functional theory (DFT). Dopants that occur in olivine minerals were considered and consisted of Ca, Sr, and Ba for the AE dopants and Cr, Mn, Fe, Co, and Ni for the TM dopants. The water molecule adsorbs on the olivine surface through a metal-water bond (Me-Ow) and a hydrogen bond with an adjacent surface lattice oxygen (Ox-Hw). A frontier orbital analysis reveals that the 1b2, 3a1, and 1b1 (HOMO) of the water molecule are involved in the bonding. All of the TM dopants show strong net Me-Ow covalent bonding between 3a1 and 1b1 water orbitals and TM d states, while the AE dopants except for Mg2SiO4(010) show negligible Me-Ow covalent bonding. Both the AE and TM dopants show similar hydrogen bonding features involving both the 1b2 and 3a1 orbitals. While the AE cations show an overall lower Me-Ow covalent interaction, the AE dopants have strong electrostatic interactions between the positive metal cation and the negatively charged water dipole. A bonding model incorporating a linear combination of the covalent Me-Ow bond, the Ox-Hw hydrogen bond, the electrostatic interaction between the dopant cation and the H2O molecule, and the surface distortion energy is needed to capture the variation in the DFT adsorption energies on the olivine surfaces. The bonding analysis is able to identify the dominant contributions to water-dopant interactions and can serve as a basis for future studies of more realistic water-olivine interfaces.