Structural, electronic, stability and reduction properties of perovskite surfaces: The case of rhombohedral BaCeO3

► The rhombohedral BaCeO3 structure is optimized using DFT + U method. ► Formation of (100) surfaces of BaCeO3 via crystal cleavage is found more favorable than (110) and (111) surfaces. ► The BaO(100) and BaCeO(110) are only the stable terminations with respect to decomposition into constituent oxides and metals. ► CeO2(100) and O(110) terminations have the lowest vacancy formation energies.