Hartree-Fock study of phase changes in ZnO at high pressure

Abstract

The total energy of ZnO as a function of unit cell volume has been calculated for the zinc-blende, wurtzite, and rocksalt structures by the ab initio all-electron periodic Hartree-Fock linear-combination-of-atomic-orbitals method using a large Gaussian basis set that was variationally optimized for the solid state. Extensive convergence tests with respect to cutoffs of the real-space Coulomb and exchange series were carried out to ensure that the calculations were performed with sufficient precision. The calculated structural properties (equilibrium lattice constant, bulk modulus, etc.) of the wurtzite and rocksalt phases are in good agreement with experiment, as is the transition pressure between them (8.57 GPa versus 9--9.5 GPa experimentally), indicating that the method can reliably predict quite small energy differences between different densities or crystal structures of a nonmetallic solid. The calculated valence-band structure was also in satisfactory agreement with experiment. Detailed analysis of the charge-density distribution supports the expected picture of a transition from mixed ionic-covalent bonding in the tetrahedrally coordinated structures to predominantly ionic bonding in the high-pressure phase.