DOE OSTI2018
Re-based double perovskites (DPs) have garnered substantial attention due to their high Curie temperatures (T C ) and display of complex interplay of structural and metal-insulator transitions (MIT). In this report we systematically study the ground-state electronic and structural properties for a family of Re-based DPs A 2 BReO 6 (A=Sr, Ca and B=Cr, Fe), which are related by a common low-energy Hamiltonian, using density functional theory +U calculations. We show that the on-site interaction U of Re induces orbital ordering (denoted C-OO), with each Re site having an occupied d xy orbital and a C-type alternation among d xz /d yz , resulting in an insulating state consistent with experimentally determined insulators Sr 2 CrReO 6 , Ca 2 CrReO 6 , and Ca 2 FeReO 6 . The threshold value of U Re for orbital ordering is reduced by inducing E g octahedral distortions of the same C-type wavelength (denoted C-OD), which serves as a structural signature of the orbital ordering; octahedral tilting also reduces the threshold. The C-OO and the concomitant C-OD are a spontaneously broken symmetry for the Sr-based materials (i.e., a 0 a 0 c - tilt pattern), while not for the Ca-based systems (i.e., a - a - b + tilt pattern). Spin-orbit coupling does not qualitatively change the physics of the C-OO/C-OD, but can induce relevant quantitative changes. We prove that a single set of U Cr , U Fe , U Re capture the experimentally observed metallic state in Sr 2 FeReO 6 and insulating states in other three systems. We predict that the C-OO is the origin of the insulating state in Sr 2 CrReO 6 , and that the concomitant C-OD may be experimentally observed at sufficiently low temperatures (i.e., space group P4 2 /m) in pure samples. Additionally, given our prescribed values of U, we show that the C-OO induced insulating state in Ca 2 CrReO 6 will survive even if the C-OD amplitude is suppressed (e.g., due to thermal fluctuations). The role of the C-OO/C-OD in the discontinuous, temperature driven MIT in Ca 2 FeReO 6 is discussed.