Electronic structure of the magnetic halide double perovskites Cs2(Ag,Na)FeCl6 from first principles

Abstract

A family of magnetic halide double perovskites (HDPs) have recently attracted attention due to their potential to broaden application areas of halide double perovskites into, e.g., spintronics. Up to date the theoretical modeling of these systems have relied on primitive approximations to the density functional theory (DFT). In this paper, we study structural, electronic and magnetic properties of the Fe3+-containing HDPs Cs2AgFeCl6 and Cs2NaFeCl6 using a combination of more advanced DFT-based methods, including DFT+U, hybrid-DFT, and treatments of various magnetic states. We examine the effect of varying the effective Hubbard parameter, Ueff, in DFT+U and the mixing-parameter, α, in hybrid DFT on the electronic structure and structural properties. Our results reveal a set of localized Fe(d) states that are highly sensitive to these parameters. Cs2AgFeCl6 and Cs2NaFeCl6 are both antiferromagnets with Neél temperatures well below room temperature and are thus in their paramagnetic (PM) state at the external conditions relevant to most applications. Therefore, we have examined the effect of disordered magnetism on the electronic structure of these systems and find that while Cs2NaFeCl6 is largely unaffected, Cs2AgFeCl6 shows significant renormalization of its electronic band structure.