Diffusion quantum Monte Carlo calculations of SrFeO₃ and LaFeO₃

The equations of state, formation energy, and migration energy barrier of the oxygen vacancy in SrFeO₃ and LaFeO₃ were calculated with the diffusion quantum Monte Carlo (DMC) method. Calculations were also performed with various Density Functional Theory (DFT) approximations for comparison. DMC reproduces the measured cohesive energies of these materials with errors below 0.23(5) eV and the structural properties within 1% of the experimental values. The DMC formation energies of the oxygen vacancy in SrFeO₃ and LaFeO₃ under oxygen-rich conditions are 1.3(1) and 6.24(7) eV, respectively. Similar calculations with semi-local DFT approximations for LaFeO₃ yielded vacancy formation energies 1.5 eV lower. Comparison of charge density evaluated with DMC and DFT approximations shows that DFT tends to overdelocalize the electrons in defected SrFeO₃ and LaFeO₃. Calculations with DMC and local density approximation yield similar vacancy migration energy barriers, indicating that steric/electrostatic effects mainly determine migration barriers in these materials.