Electronic and Polar Properties of Vanadate Compounds Stabilized by Epitaxial Strain Thomas Angsten Lane W. Martin Mark Asta 10.1021/acs.chemmater.8b01499.s003 https://acs.figshare.com/articles/dataset/Electronic_and_Polar_Properties_of_Vanadate_Compounds_Stabilized_by_Epitaxial_Strain/7005851 Recent experimental and computational studies have demonstrated pressure and epitaxial stabilization of polar PbVO<sub>3</sub> phases with perovskite-derivative crystal structures. In this study, we demonstrate, by density functional theory (DFT) calculations, the stability of similar perovskite-derivative structures in the KVO<sub>3</sub> and NaVO<sub>3</sub> systems when subjected to compressive biaxial strain. The electronic structure and polar properties of these compounds are computed as a function of biaxial strain, and the results are compared to those obtained for experimentally observed PbVO<sub>3</sub> structures. It is demonstrated that the substitution of Pb with monovalent K or Na cations increases the strength of the vanadyl bond due to the removal of the spatially extended Pb 6p states. Both KVO<sub>3</sub> and NaVO<sub>3</sub> exhibit epitaxially stabilized perovskite-derivative phases having large polarizations and only small total energy increases relative to their unstrained bulk structures. The calculated epitaxial phase diagram for KVO<sub>3</sub> predicts a strain-energy driving force for a phase separation from −4% to 1.5% misfit strain into a polar <i>Cm</i> phase, having square-pyramidal coordination of the <i>B</i>-site, and a paraelectric <i>Pbcm</i> phase, having tetrahedral coordination of the <i>B</i>-site. The results show that strain-stabilized polar vanadate compounds may occur for other compositions in addition to PbVO<sub>3</sub> and that changes in the <i>A</i>-site species can be used to tune bonding, structure, and functional properties in these systems. 2018-08-10 00:00:00 NaVO 3 exhibit epitaxially Pb 6 p states biaxial strain Na cations increases epitaxial phase diagram KVO 3 PbVO 3 phases PbVO 3 structures Vanadate Compounds Stabilized unstrained bulk structures perovskite-derivative crystal structures DFT site NaVO 3 systems paraelectric Pbcm phase