Ab initio localized basis set study of structural parameters and elastic properties of HfO2 polymorphs

The SIESTA approach based on pseudopotentials and a localized basis set is used to calculate the electronic, elastic and equilibrium properties of P2(1)/c, Pbca, Pnma, Fm3m, P4(2)nmc and Pa3 phases of HfO2. Using separable Troullier-Martins norm-conserving pseudopotentials which include partial core corrections for Hf, we tested important physical properties as a function of the basis set size, grid size and cut-off ratio of the pseudo-atomic orbitals (PAOs). We found that calculations in this oxide with the LDA approach and using a minimal basis set (simple zeta, SZ) improve calculated phase transition pressures with respect to the double-zeta basis set and LDA (DZ-LDA), and show similar accuracy to that determined with the PPPW and GGA approach. Still, the equilibrium volumes and structural properties calculated with SZ-LDA compare better with experiments than the GGA approach. The bandgaps and elastic and structural properties calculated with DZ-LDA are accurate in agreement with previous state of the art ab initio calculations and experimental evidence and cannot be improved with a polarized basis set. These calculated properties show low sensitivity to the PAO localization parameter range between 40 and 100 meV However, this is not true for the relative energy, which improves upon decrease of the mentioned parameter. We found a non-linear behaviour in the lattice parameters with pressure in the P2(1)/c phase, showing a discontinuity of the derivative of the a lattice parameter with respect to external pressure, as found in experiments. The common enthalpy values calculated with the minimal basis set give pressure transitions of 3.3 and 10.8 GPa for P2(1)/c -> Pbca and Pbca -> Pnma, respectively, in accordance with different high pressure experimental values.