title: Polar surface energies of iono-covalent materials: implications of a charge-transfer model tested on Li2FeSiO4 surfaces.
abstract: The ionic compounds that are used as electrode materials in Li-based rechargeable batteries can exhibit polar surfaces that in general have high surface energies. We derive an analytical estimate for the surface energy of such polar surfaces assuming charge redistribution as a polarity compensating mechanism. The polar contribution to the converged surface energy is found to be proportional to the bandgap multiplied by the surface charge necessary to compensate for the depolarization field, and some higher order correction terms that depend on the specific surface. Other features, such as convergence behavior, coincide with published results. General conclusions are drawn on how to perform polar surface energy calculations in a slab configuration and upper boundaries of "purely" polar surface energies are estimated. Furthermore, we compare these findings with results obtained in a density functional theory study of Li(2)FeSiO(4) surfaces. We show that typical polar features are observed and provide a decomposition of surface energies into polar and local bond-cutting contributions for 29 different surfaces. We show that the model is able to explain subtle differences of GGA and GGA+U surface energy calculations.
authors.affiliation: Helmholtz Institute Ulm Electrochemical Energy Storage, Albert-Einstein-Allee 11, 89069 Ulm (Germany); Universität Ulm, Institut für Theoretische Chemie, Albert-Einstein-Allee 11, 89069 Ulm (Germany).
authors.forename: Nicolas G
authors.initials: NG
authors.lastname: Hörmann
authors.forename: Axel
authors.initials: A
authors.lastname: Groß
keywords: computational chemistry; electrochemistry; energy storage; ionic compounds; surface structure