Polaronic Hole Trapping in Doped BaBiO3

The present ab initio study shows that in BaBiO3, Bi3+ sites can trap two holes from the valence band to form Bi5+ cations. The trapping is accompanied by large local lattice distortions; therefore the composite particle consisting of the electronic hole and the local lattice phonon field forms a polaron. Our study clearly shows that even sp elements can trap carriers at lattice sites, if local lattice relaxations are sufficiently large to screen the localized hole. The derived model describes all relevant experimental results, and settles the issue of why hole-doped BaBiO3 remains semiconducting upon moderate hole doping.