Jahn–Teller and spin–orbit coupling effects in transition-metal trifluorides

Mondal, Padmabati; Opalka, Daniel; Poluyanov, Leonid V.; Domcke, Wolfgang

doi:10.1016/j.chemphys.2011.06.034

Cited by 43 publications

(50 citation statements)

References 63 publications

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“…In this case, the effect is referred to as dynamical J‐T distortion and only the superposition of all distorted structures (i.e., the spherically symmetric nondistorted structure) is possible to observe. In previous theoretical studies, MnF 3 , CoF 3 , and NiF 3 have been found to show a dynamical J‐T distortion in their molecular form . We emphasize that this work considers only static J‐T distortions.…”

Section: Resultsmentioning

confidence: 90%

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

Mattsson

Paulus

2019

J Comput Chem

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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 .

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Section: Resultsmentioning

confidence: 90%

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

Mattsson

Paulus

2019

J Comput Chem

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“…Herein, we have noticed that the Jahn–Teller effect plays a key role in the phase transition of

{Sc}_{1 - x} {Ti}_{x} {normalF}_{3}

, and is also responsible for controlling the thermal expansion. As far as we know, the Jahn–Teller effect can be also observed in other transition‐metal trifluorides such as VF 3 , MnF 3 , CoF 3 , and NiF 3 . It is inspired that maybe the doping of these Jahn–Teller active trivalent cations will also be an effective approach to tune the thermal expansion of Sc 1‐x M x F 3 .…”

Section: Resultsmentioning

confidence: 91%

“…In

{Sc}_{1 - x} {Ti}_{x} {normalF}_{3}

, the

{Ti}^{3 +}

can introduce the Jahn–Teller effect . In cubic framework structure, each Sc atom is at the center of a corner sharing fluoride atoms, forming an octahedral coordination environment.…”

Section: Resultsmentioning

confidence: 99%

First‐Principles Study of Sc_1−xTi_xF₃ (x ≤ 0.375): Negative Thermal Expansion, Phase Transition, and Compressibility

Wang

Sun

et al. 2015

J. Am. Ceram. Soc.

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We present the first‐principles investigation of boldSc1−xboldTiboldxboldFbold3 (x ≤ 0.375). Controllable thermal expansion of boldSc1−xboldTiboldxboldFbold3 is achieved by different Ti contents. The negative thermal expansion (NTE) behavior is weakened gradually with increasing Ti content, which is consistent with experimental measurements. The Jahn–Teller effect plays an important role in the cubic‐to‐rhombohedral phase transition, which stems from the enhanced energy stability when the 3d orbitals of Tibold3+ cation split into triply degenerate tbold2boldg and eg sets. The unusual thermal stiffening of boldSc1−xTixnormalF3 is found, which is similar to that of boldSc1−xboldYboldxboldFbold3 and boldSc1−xboldAlboldxboldFbold3 but contrary to other NTE materials.

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“…For example, JT/pJT-active bending vibrations can bring nuclei close to each other and the resultant repulsion features positive anharmonicity. 10,11,13,14 This is the so-called intramolecular collision. 15 Also, when a JT/pJT problem involves bond dissociation, the diabatic potentials are anharmonic and require higher order expansions.…”

Section: Introductionmentioning

confidence: 99%

General formalism for vibronic Hamiltonians in tetragonal symmetry and beyond

Hickman

Lang

Zeng

2018

Phys. Chem. Chem. Phys.

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We derive general expansion formulas in vibrational coordinates for all bimodal Jahn-Teller and pseudo-Jahn-Teller Hamiltonians in tetragonal symmetry. Symmetry information of all the vibronic Hamiltonian matrix elements is fully carried by up to only 4 eigenvalues of symmetry operators. This problem-to-eigenvalue reduction enables us to handle thousands of vibronic problems in one work. The derived bimodal formulas can be easily extended to cover problems with one or more than two vibrational modes. They lay a solid foundation for future vibronic coupling studies of tetragonal systems. More importantly, the efficient derivation can be applied to handle (pseudo-)Jahn-Teller Hamiltonians for all problems with one principal symmetry axis.

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Jahn–Teller and spin–orbit coupling effects in transition-metal trifluorides

Cited by 43 publications

References 63 publications

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

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

First‐Principles Study of Sc_1−xTi_xF₃ (x ≤ 0.375): Negative Thermal Expansion, Phase Transition, and Compressibility

General formalism for vibronic Hamiltonians in tetragonal symmetry and beyond

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Jahn–Teller and spin–orbit coupling effects in transition-metal trifluorides

Cited by 43 publications

References 63 publications

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

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

First‐Principles Study of Sc1−xTixF3 (x ≤ 0.375): Negative Thermal Expansion, Phase Transition, and Compressibility

General formalism for vibronic Hamiltonians in tetragonal symmetry and beyond

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

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

First‐Principles Study of Sc_1−xTi_xF₃ (x ≤ 0.375): Negative Thermal Expansion, Phase Transition, and Compressibility