Atomic and electronic structure of unreduced and reduced CeO2 surfaces: a first-principles study.

The atomic and electronic structure of (111), (110), and (100) surfaces of ceria (CeO2) were studied using density-functional theory within the generalized gradient approximation. Both stoichiometric surfaces and surfaces with oxygen vacancies (unreduced and reduced surfaces, respectively) have been examined. It is found that the (111) surface is the most stable among the considered surfaces, followed by (110) and (100) surfaces, in agreement with experimental observations and previous theoretical results. Different features of relaxation are found for the three surfaces. While the (111) surface undergoes very small relaxation, considerably larger relaxations are found for the (110) and (100) surfaces. The formation of an oxygen vacancy is closely related to the surface structure and occurs more easily for the (110) surface than for (111). The preferred vacancy location is in the surface layer for CeO2(110) and in the subsurface layer (the second O-atomic layer) for CeO2(111). For both surfaces, the O vacancy forms more readily than in the bulk. An interesting oscillatory behavior is found for the vacancy formation energy in the upper three layers of CeO2(111). Analysis of the reduced surfaces suggests that the additional charge resulting from the formation of the oxygen vacancies is localized in the first three layers of the surface. Furthermore, they are not only trapped in the 4f states of cerium.