Comparative density-functional LCAO and plane-wave calculations of LaMnO3 surfaces -: art. no. 214411

We compare two approaches to the atomic, electronic, and magnetic structures of LaMnO3 bulk and the ( 001 ), ( 110 ) surfaces - hybrid B3PW with optimized LCAO basis set ( CRYSTAL- 2003 code ) and GGA- PW91 with plane- wave basis set ( VASP 4.6 code ). Combining our calculations with those available in the literature, we demonstrate that combination of nonlocal exchange and correlation used in hybrid functionals allows to reproduce the experimental magnetic coupling constants J(ab) and J(c) as well as the optical gap. Surface calculations performed by both methods using slab models show that the antiferromagnetic ( AF ) and ferromagnetic ( FM ) ( 001 ) surfaces have lower surface energies than the FM ( 110 ) surface. Both the ( 001 ) and ( 110 ) surfaces reveal considerable atomic relaxations, up to the fourth plane from the surface, which reduce the surface energy by about a factor of 2, being typically one order of magnitude larger than the energy difference between different magnetic structures. The calculated ( Mulliken and Bader ) effective atomic charges and the electron density maps indicate a considerable reduction of the Mn and O atom ionicity on the surface.