Charge-transfer electrostatic model of compositional order in perovskite alloys

Abstract

We introduce an electrostatic model including charge transfer, which is shown to account for the observed B-site ordering in Pb-based perovskite alloys. The model allows charge transfer between A-sites and is a generalization of Bellaiche and Vanderbilt's purely electrostatic model. The large covalency of Pb^{2+} compared to Ba^{2+} is modeled by an environment dependent effective A-site charge. Monte Carlo simulations of this model successfully reproduce the long range compositional order of both Pb-based and Ba-based complex A(BB^{'}B^{''})O_3 perovskite alloys. The models are also extended to study systems with A-site and B-site doping, such as (Na_{1/2}La_{1/2})(Mg_{1/3}Nb_{2/3})O_3, (Ba_{1-x}La_{x})(Mg_{(1+x)/3}Nb_{(2-x)/3})O_3 and (Pb_{1-x}La_{x})(Mg_{(1+x)/3}Ta_{(2-x)/3})O_3. General trends are reproduced by purely electrostatic interactions, and charge transfer effects indicate that local structural relaxations can tip the balance between different B-site orderings in Pb based materials.