Structural and metal-insulator transitions in rhenium-based double perovskites via orbital ordering

Abstract

Re-based double perovskites (DPs) exhibit a complex interplay of structural and metal-insulator transitions. Here we systematically study the ground state electronic and structural properties for a family of Re-based DPs $A_2B$ReO$_6$ ($A$=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 COO), 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 COD), which serves as a structural signature of the orbital ordering; octahedral tilting also reduces the threshold. The COO, and the concomitant COD, are a spontaneously broken symmetry for the Sr based materials (i.e. $a^0a^0c^-$ 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 COO/COD, 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 the other three systems. We predict that the COO is the origin of the insulating state in Sr$_2$CrReO$_6$, and that the concomitant COD may be experimentally observed at sufficiently low temperatures (ie. space group P$4_2/m$). Additionally, given our prescribed values of $U$, we show that the COO induced insulating state in Ca$_2$CrReO$_6$ will survive even if the COD amplitude is suppressed (e.g. due to thermal fluctuations).