Molecular modeling of the surface charging of hematite: II. Optimal proton distribution and simulation of surface charge versus pH relationships

• Published in: Surface science 1999-03, Vol.424 (1), p.28-35
• Main Authors: Rustad, James R., Wasserman, Evgeny, Felmy, Andrew R.
• Format: Article
• Language: English
• Subjects: Condensed matter: electronic structure, electrical, magnetic, and optical properties; Electronic structure and electrical properties of surfaces, interfaces, thin films and low-dimensional structures; Exact sciences and technology; Hematite; Impurity and defect levels; energy states of adsorbed species; Molecular modeling; pH relationships; Physics; Proton distribution; Surface and interface electron states; Surface charge
• ISSN: 0039-6028; 1879-2758
• DOI: 10.1016/S0039-6028(99)00009-6

A parameterized classical potential model for the interaction of water and hydroxide with iron oxide was used to calculate the optimal proton arrangement and proton binding energies on the (012) surface of hematite. Energy minimization calculations with the parameterized potential model indicate that approximately 75% of adsorbed water molecules are dissociated on this surface, in agreement with recent TPD and HREELS measurements. Surface protonation/deprotonation energies were calculated from the predicted optimal arrangement of protons on the neutral (012) surface. A supercell geometry with translational symmetry in two dimensions and finite in the third dimension (2-D PBC) was assumed. The calculated surface protonation energies were then used to model the experimentally observed surface-charging curve of hematite in aqueous solution. Excellent agreement was found between the calculated and measured surface charge for ionic strengths ranging from 0.001 to 0.1 M. Our calculations favor the value of 8.5 for the pH of zero charge of hematite over the more recent result of 6.7.