Lattice vibrations and energy landscape of the isoelectronic semiconductor series CuBr, ZnSe, GaAs, and Ge: The special case of CuBr and its d-level chemistry

We have examined the lattice vibrations and the energy landscape of the isoelectronic diamond and zincblende semiconductor series CuBr, ZnSe, GaAs, and Ge. Vibrations are found to be an increasing function of ionicity, with the cation sublattice always vibrating more strongly than the anion sublattice. These findings are consistent with density functional theory (DFT) calculations of the energy landscape and temperature-dependent molecular dynamics simulations of the atomic-position fluctuations. For CuBr, inclusion of the Cu 3d Hubbard U term is found necessary to stabilize the zincblende structure and to bring its vibrational amplitudes into agreement with experiment. In addition, vibrations are found to strongly affect the CuBr near-edge x-ray absorption fine structure that we have successfully modeled by including displacements in our theoretical Bethe-Salpeter equation calculations. Reverse Monte Carlo structural refinements using large atomic configurations to simultaneously fit x-ray absorption and x-ray total-scattering data support these conclusions, and they reveal strong Cu-Br first-neighbor correlations and asymmetric distributions of interatomic distances in the temperature ranges of both negative and positive thermal expansion. Delineation of the CuBr valence band photoelectron spectrum into its Cu 3d and Br 4p states uniquely reveals their covalent mixing and further supports the DFT results.