Structural, vibrational, and quasiparticle properties of the Peierls semiconductor BaBiO3: A hybrid functional and self-consistent GW+vertex-corrections study

BaBiO3 is characterized by a charge disproportionation with half of the Bi atoms possessing a valence 3+ and half a valence 5+. Because of self-interaction errors, local- and semilocal-density functionals fail to describe the charge disproportionation quantitatively, yielding a too small structural distortion and no band gap. Using hybrid functionals, we obtain a satisfactory description of the structural, electronic, optical, and vibrational properties of BaBiO3. The results obtained using GW (Green's function G and screened Coulomb potential W) based schemes on top of hybrid functionals, including fully self-consistent GW calculations with vertex corrections in the dielectric screening, qualitatively confirm the Heyd-Scuseria-Ernzerhof picture but a systematic overestimation of the band gap by about 0.4 eV is observed. © 2010 The American Physical Society.