Density Functional Theory Calculations of Structural, Electronic, and Magnetic Properties of the 3d Metal Trifluorides MF₃ (M = Ti‐Ni) in the Solid State

Abstract

We employ density functional theory with Hubbard U correction or hybrid functionals to study the series of magnetic 3d metal trifluorides MF 3 (M = Ti‐Ni). Experimental lattice parameters are reproduced with an error margin of 0.5%–4.3%. Cooperative Jahn–Teller distortions are reproduced for MnF 3 , but also found in TiF 3 and CoF 3 at smaller levels compared to MnF 3 . Trends in electronic structure with respect to positions of the d bands are linked to the magnetic properties where M = Ti‐Cr are weak magnetic Mott–Hubbard insulators, M = Fe‐Ni are strong magnetic charge‐transfer insulators and MnF 3 falls in between. Our work contributes to the characterization of the relatively unknown NiF 3 , since FeF 3 and CoF 3 have similar electronic and magnetic properties. However, NiF 3 does not show a Jahn–Teller distortion as present in CoF 3 . © 2019 Wiley Periodicals, Inc.