Theoretical studies of the concentration dependences of d–d transition band, g factors, and local distortion for V4+ in Li2O–PbO–B2O3–P2O5 glasses

Lyu, Jun-Rui; Wu, Shao-Yi; Hong, Yu-Jing; Wu, Hao; Dong, Hui

doi:10.1002/mrc.5232

Cited by 3 publications

(1 citation statement)

References 39 publications

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“…Secondly, the empirical relationship Ā2 (R)/ Ā4 (R) ≈ 10.8 applied in the calculations of tetragonal CF parameters may bring some errors to the compression ratio ρ and hence the g-factors (note that the relationship Ā2 (R)/ Ā4 (R) ≈ 9 ∼ 12 for d n ions has been proved to be valid in many theoretical works [29,31,33,40,[42][43][44][45][46][47]). According to our calculations, the errors of the final g-factors and the relative compression ratio ρ are estimated not to exceed 1% and 6% (see Fig.…”

Section: Discussionmentioning

confidence: 99%

Theoretical studies on the g-factors and the local structure of W5+ ions in tungsten phosphate glasses

et al. 2023

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In this work, we adopt the three-order perturbation formulae for g-factors (g//, g^) of d1 ions in the octahedral environment to calculate the g-factors of W5+ ions in tungsten phosphate glasses containing lithium (P2O5-Li2WO4-Li2O). In the light of the high valence state of the studied W5+ centers and hence the strong covalency of the studied octahedral [WO6]7- cluster, we consider the contributions to g-factors from the ligand orbital and spin-orbit (SO) coupling interactions based on the cluster approach. The required tetragonal crystal-field parameters are calculated from the local structure of W5+ ions based on the superposition model. According to the theoretical calculations, we find that the octahedral [WO6]7- clusters possess the tetragonally compressed distortion with a shorter W-O bond length (≈1.54 Å) and a longer one (≈2.26 Å) along C4 axis and four normal W-O bond length (≈1.94 Å) in the perpendicular plane, which infers that the W5+ ions are in the form of tungstyl ions (i.e., WO3-). Based on the local structural data, the theoretical values of g// and g^ agree well with the experimental values.

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Section: Discussionmentioning

confidence: 99%

Theoretical studies on the g-factors and the local structure of W5+ ions in tungsten phosphate glasses

et al. 2023

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Studies on the EPR parameters and local angular distortion for the tetragonal Cu²⁺ center in CaWO₄ crystal

Chen

Yao

Feng

et al. 2022

Magnetic Reson in Chemistry

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The electron paramagnetic resonance (EPR) parameters-g factors g i (i = jj and ⊥) and hyperfine structure constants A i (M) and A i (N), with M and N belonging to isotopes 63 Cu 2+ and 65 Cu 2+ -and local structure of Cu 2+ ion occupying W 6+ site in CaWO 4 crystal are theoretically studied based on the perturbation formulas of these parameters for a 3d 9 ion under tetragonally elongated tetrahedra. In these formulas, the ligand orbital (LO) and spin-orbit coupling (SOC) contributions are included due to the shorter impurity-ligand distance R (≈1.83 Å) and hence the strong covalency of the studied [CuO 4 ] 6À cluster, and the related molecular orbital coefficients are quantitatively determined from the cluster approach in a uniform way; meanwhile, the required crystal field (CF) parameters for the tetragonally distorted tetrahedron (TDT) are estimated from the superposition model and the local structure of the impurity Cu 2+ center. According to the calculation, the bond angle θ between the four equivalent Cu 2+ -O 2À bonds and the C 4 axis in the CaWO 4 :Cu 2+ is found to be about 2.1 smaller than that (θ 0 ≈ 54.74 ) for an ideal tetrahedron due to the Jahn-Teller (JT) effect and the size mismatch. The fitted results agree well with the observed values, and the validity of the present assignment for the local structure of the Cu 2+ center is also discussed.

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Investigations on the EPR parameters and local structures for the substitutional Ti³⁺ and W⁵⁺ centers in stishovite

Chen,

Zhou,

Zhang

et al. 2024

Zeitschrift Für Naturforschung A

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Local structures and electron paramagnetic resonance (EPR) parameters (g factors g x , g y , and g z ) for the substitutional Ti3+ and W5+ centers in stishovite are theoretically investigated by using the high-order perturbation formulas of these parameters for a d1 ion in rhombically compressed octahedra. In the calculation formulas, the related molecular orbital coefficients are obtained from the cluster approach, and the relevant crystal-field (CF) parameters are determined from the superposition model, which enables to connect these CF parameters and, hence, the studied g factors with the local structures of the Ti3+ and W5+ centers in stishovite. Based on the calculations, the impurity–ligand bond lengths parallel and perpendicular to the C 2-axis are found to be R′|| (≈1.751 and 1.717 Å) and R′⊥ (≈1.788 and 1.806 Å) with the planar bond angles θ′ (≈89.0° and 88.2°) for the studied [TiO6]9− and [WO6]7− clusters, respectively. The calculated results are in good agreement with the experimental data, and the validity of the results is discussed.

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Theoretical studies of the concentration dependences of d–d transition band, g factors, and local distortion for V⁴⁺ in Li₂O–PbO–B₂O₃–P₂O₅ glasses

Cited by 3 publications

References 39 publications

Theoretical studies on the g-factors and the local structure of W5+ ions in tungsten phosphate glasses

Theoretical studies on the g-factors and the local structure of W5+ ions in tungsten phosphate glasses

Studies on the EPR parameters and local angular distortion for the tetragonal Cu²⁺ center in CaWO₄ crystal

Investigations on the EPR parameters and local structures for the substitutional Ti³⁺ and W⁵⁺ centers in stishovite

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Theoretical studies of the concentration dependences of d–d transition band, g factors, and local distortion for V4+ in Li2O–PbO–B2O3–P2O5 glasses

Cited by 3 publications

References 39 publications

Theoretical studies on the g-factors and the local structure of W5+ ions in tungsten phosphate glasses

Theoretical studies on the g-factors and the local structure of W5+ ions in tungsten phosphate glasses

Studies on the EPR parameters and local angular distortion for the tetragonal Cu2+ center in CaWO4 crystal

Investigations on the EPR parameters and local structures for the substitutional Ti3+ and W5+ centers in stishovite

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Theoretical studies of the concentration dependences of d–d transition band, g factors, and local distortion for V⁴⁺ in Li₂O–PbO–B₂O₃–P₂O₅ glasses

Studies on the EPR parameters and local angular distortion for the tetragonal Cu²⁺ center in CaWO₄ crystal

Investigations on the EPR parameters and local structures for the substitutional Ti³⁺ and W⁵⁺ centers in stishovite