Angsten, Thomas Martin, Lane W. Asta, Mark Electronic and Polar Properties of Vanadate Compounds Stabilized by Epitaxial Strain 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. 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 2018-08-10
    https://acs.figshare.com/articles/dataset/Electronic_and_Polar_Properties_of_Vanadate_Compounds_Stabilized_by_Epitaxial_Strain/7005851
10.1021/acs.chemmater.8b01499.s003