title: Adsorption of atomic and molecular oxygen on the LaMnO3(001) surface: ab initio supercell calculations and thermodynamics.
abstract: We present and discuss the results of ab initio DFT plane-wave supercell calculations of the atomic and molecular oxygen adsorption and diffusion on the LaMnO(3) (001) surface which serves as a model material for a cathode of solid oxide fuel cells. The dissociative adsorption of O(2) molecules from the gas phase is energetically favorable on surface Mn ions even on a defect-free surface. The surface migration energy for adsorbed O ions is found to be quite high, 2.0 eV. We predict that the adsorbed O atoms could penetrate the electrode first plane when much more mobile surface oxygen vacancies (migration energy of 0.69 eV) approach the O ions strongly bound to the surface Mn ions. The formation of the O vacancy near the O atom adsorbed atop surface Mn ion leads to an increase of the O-Mn binding energy by 0.74 eV whereas the drop of this adsorbed O atom into a vacancy possesses no energy barrier. Ab initio thermodynamics predicts that at typical SOFC operation temperatures (approximately 1200 K) the MnO(2) (001) surface with adsorbed O atoms is the most stable in a very wide range of oxygen gas pressures (above 10(-2) atm).
authors.affiliation: Max Planck Institute for Solid State Research, Heisenbergstrasse 1, Stuttgart, Germany. sofia.weiglein@fkf.mpg.de
authors.forename: Eugene A
authors.initials: EA
authors.lastname: Kotomin
authors.forename: Yuri A
authors.initials: YA
authors.lastname: Mastrikov
authors.forename: Eugene
authors.initials: E
authors.lastname: Heifets
authors.forename: Joachim
authors.initials: J
authors.lastname: Maier