The cation ratios in the (100) surface of cubic oxides of bulk composition A0.99B0.01O, in which A and B are divalent cations were calculated using a monolayer model. Divalent cations including Ni, Co, Mn, Fe and Mg were studied. The cations were represented by a shell model, and the surface compositions were calculated by minimizing the total Gibbs free energy of the solid. The bulk energy change on surface segregation was evaluated by minimizing the energy change on substituting one bulk cation by another in an infinitely dilute solid solution and the surface energy was evaluated by a statistical method to accommodate the possibility that both cations can exist at non-negligible densities at the surface. The bulk energy change on surface segregation was found to be dominant in most cases. The surface energy change, the entropy change, and the change in crystal field stabilization energy were all secondary. Thus, except when the difference in ionic radii is very small, the larger cation is always more preferred at the surface. This conclusion appears to be in agreement with available experimental data.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Condensed Matter Physics
- Surfaces and Interfaces