First-principles calculation of the electronic and optical properties of Gd$_{2}$FeCrO$_{6}$ double perovskite: Effect of Hubbard U parameter

Published 2 Nov 2021 in cond-mat.mtrl-sci | (2111.01864v1)

Abstract: We have synthesized Gd${2}$FeCrO${6}$ (GFCO) double perovskite which is crystallized in a monoclinic structure with P2${1}/$n space group. The UV-visible and photoluminescence spectroscopic analyses confirmed its direct bandgap semiconducting nature. Employing experimentally obtained structural parameters in first-principles calculation, we report the spin-polarized electronic band structure, charge carrier effective mass, density of states, electronic charge density distribution and optical absorption property of the GFCO double perovskite. The effects of on-site d-d Coulomb interaction energy (U${eff}$) on the electronic and optical properties were investigated by applying a range of Hubbard U${eff}$ parameters from 0 to 6 eV to the Fe-3d and Cr-3d orbitals within the generalized gradient approximation (GGA) and GGA+U methods. When we applied U${eff}$ in the range of 1 to 5 eV, both the up-spin and down-spin band structures were observed to be direct. The charge carrier effective masses were also found to enhance gradually from U${eff} =$ 1 eV to 5 eV, but, these values were anomalous for U${eff} =$ 0 and 6 eV. These results suggest that U${eff}$ should be limited within the range of 1 to 5 eV to calculate the structural, electronic and optical properties of GFCO double perovskite. We observed that considering U${eff} =$ 3 eV, the theoretically calculated optical band gap 1.99 eV matched well with the experimentally obtained value 2.0 eV. The outcomes of our finding imply that the U${eff}$ value of 3 eV most accurately localized the Fe-3d and Cr-3d orbitals of GFCO keeping the effect of self-interaction error from the other orbitals almost negligible. Therefore, we may recommend U${eff} =$ 3 eV for first-principles calculation of the electronic and optical properties of GFCO double perovskite that might have potential in photocatalytic and related solar energy applications.