The local structure, electronic and optical properties of Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_3$-PbTiO$_3$: first-principles study

Abstract: Pb(Mg${1/3}$Nb${2/3}$)O$3$-PbTiO$_3$ perovskite-based crystals attract considerable scientific interest due to their interesting properties and possible use in piezoelectricity and photovoltaics. To understand the local structure and fundamental properties of such materials, in this work, we focused on the study within the density functional theory of structural, electronic, and optical properties of Pb[(Mg${1/3}$Nb${2/3}$)${0.75}$Ti${0.25}$]O$_3$. Using GGA(PBEsol) approximation for structure optimization gives a good agreement with experimental data. Through the variation in Hubbard $U$ parameters to GGA(PBEsol) functional, we achieve the bandgap for the Pb[(Mg${1/3}$Nb${2/3}$)${0.75}$Ti${0.25}$]O$_3$ which is in good agreement with the experimental results. The study of the bond populations showed that the Mg-O bond demonstrates no covalency, whereas there is a significant Ti-O and Nb-O covalent bonding. Such different bonding characteristics must be responsible for the relaxor properties of Pb[(Mg${1/3}$Nb${2/3}$)${0.75}$Ti${0.25}$]O$_3$ compound. In addition, the investigations of the optical properties of the Pb[(Mg${1/3}$Nb${2/3}$)${0.75}$Ti$_{0.25}$]O$_3$ by adopting Hubbard $U$ corrections, modifying the error of the GGA approximation, and confirming the electronic analysis, were performed.