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 .

Combining Theory and Experiment to Characterize the Voltammetric Behavior of Nickel Anodes in the Simons Process

“…All Ni 3+ centers (d 7 ) are characterized by their magnetic moment, which, owing to the high‐spin configuration, varies between 2.14 μ B and 2.18 μ B . This is in good agreement with the corresponding magnetic moment of 2.30 μ B in crystalline NiF 3 , which was calculated with HSE06 …”

“…This increases the surface CN to six (full coverage) for (1 1 0), (1 0 0), and (1 01), whereas the (0 0 1) surface has the lower CN of five. In all cases, the added F − is monodentate and its bond length varies between 1.735 and 1.715 Å, which is more consistent with the Ni−F bond length in crystalline NiF 3 (1.88 Å) than that of NiF 2 (2.02 Å; Section 1 of the Supporting Information). The very small bond lengths may be explained by the F − ion exposed to the vacuum.…”

[GaF(H2O)][IO3F]: a promising NLO material obtained by anisotropic polycation substitution

“…S10 † ) reveal an indirect band gap of 4.01 eV for [GaF(H 2 O)][IO 3 F], slightly smaller than its measured value (4.34 eV), which was caused by the discontinuity of the exchange–correlation functional. 60 Hence, a scissor value of 0.33 eV was adopted to compute the optical properties of [GaF(H 2 O)][IO 3 F]. The total and partial density of states of [GaF(H 2 O)][IO 3 F] (Fig.…”

Ba2[MoO3(OH)(IO3)2]IO3: A Promising SHG Material Featuring a Λ-Shaped Functional Motif Achieved by Universal Mono-Site Substitution

“…The band structure graph (Figure S7) shows that Ba 2 [MoO 3 (OH)­(IO 3 ) 2 ]­IO 3 has an indirect band gap of 3.30 eV, which is slightly less than the experimental value (3.78 eV). The underestimation of the band gap is mainly caused by the discontinuity of the exchange-correlation function. , A scissor value of 0.47 eV was added in the following optical analyses.…”

“…The underestimation of the band gap is mainly caused by the discontinuity of the exchange-correlation function. 64,65 A scissor value of 0.47 eV was added in the following optical analyses.…”