EPR and ENDOR spectra of copper(II) centers with dz2 and dx2-y2 ground states in barium hexafluorozincate: analysis of hyperfine parameters and dynamic vibronic coupling

Steffen, G.; Reinen, D.; Stratemeier, Horst; Riley, Mark J.; Hitchman, Michael A.; Matthies, H.; Recker, K.; Wallrafen, F.; Niklas, Juergen R.

doi:10.1021/ic00336a018

Cited by 41 publications

(49 citation statements)

References 2 publications

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“…It contributes to stabilizing the elongated with respect to the compressed D 4h conformation [10], because in the former case two electrons are lowered in energy instead of only one in the latter case. The e ds /e s ratio for the planar Cu II O 4 coordination (in Li 2 CuO 2 ) [11] and for the planar CuCl 4 2-complex [12] is found to be similar to the value above (@0.26), while it is much smaller in the case of the ionic F -ligand (≈0.07: Cu II F 4 square plane in BaCuF 4 [13]). In the CuCl 4 2-case it is remarkable that the AOM parameters are well transferable from the planar to the (D 2d -distorted) tetrahedral coordination [10].…”

Section: D-s Mixing In the Aomsupporting

confidence: 65%

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The Angular Overlap Model and Vibronic Coupling in Treating s-p and d-s Mixing – a DFT Study

Reinen

Atanasov

2004

Structure and Bonding

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The steric and energetic lone pair effect induced by s-p mixing can be parameterised within the angular overlap model (AOM), as is shown for a series of halide molecules and complexes mainly of the fifth main group (oxidation state +III) with the coordination numbers 3 to 6. The derived effective AOM parameters e sp eff , defined for the average bond lengths of the distorted structures, decrease the softer the considered entity is, and seem to be transferable within groups of chemically related species.We base the analysis on results of DFT calculations, using specifically Kohn-Sham MO diagrams in comparison to corresponding many-electron energies. There is definite experimental evidence for s-p and for d-s mixing as well, as is demonstrated by the DFT analysis of spectral data for some model complexes. The equivalence of the vibronic coupling approach on the MO level with the AOM is emphasized; the advantage of the AOM is, however, that angular and radial (bond length) contributions can be cleanly separated.

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Section: D-s Mixing In the Aomsupporting

confidence: 65%

“…1). The hyperfine interaction with the copper nucleus, particularly the isotropic contribution, is extremely sensitive to s-admixing -here induced by the a 1g *(3d z2 )-a 1g *(4s) pseudo Jahn-Teller interaction -because this implies a small unpaired electron density directly at the copper nucleus via the 1s orbital [13].…”

Section: D-s Mixing In the Aommentioning

confidence: 99%

The Angular Overlap Model and Vibronic Coupling in Treating s-p and d-s Mixing – a DFT Study

Reinen

Atanasov

2004

Structure and Bonding

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“…The value is close to the observed mean spin density f pr (&4.3 %) for the tetragonally compressed Cu 2? center in K 2 Zn 1-x Cu x F 4 [29,30]. So, the covalence parameters used seem to be reasonable.…”

Section: Discussionmentioning

confidence: 80%

“…The calculated values are in good agreement with the observed values, suggesting that the parameters (including those related to crystal-field parameters) used in above calculations are suitable. The spin density f pr can be calculated from the observed fluorine hyperfine constants [29,30], and it is related to the covalence parameters (or MO coefficients) N e and k e by the formula: f pr = 1/3 N e (k e ) 2 [31]. The spin density f pr for rhombic Cu 2?…”

Section: Discussionmentioning

confidence: 99%

Investigations of EPR g Factors and Rhombic Distortion for the Rhombic Cu2+ Centers in K2Zn1−x Cu x F4 Crystals at Low Temperature

Zheng

Zhang

et al. 2012

Appl Magn Reson

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The electron paramagnetic resonance g factors g i (i = x, y, z) of two rhombic Cu 2? centers, Cu 2? (II) and Cu 2? (III), in K 2 Zn 1-x Cu x F 4 crystals found at low temperature are calculated from the complete diagonalization (of energy matrix) method based on the cluster approach. The calculations show that the ground state wave function of the two rhombically compressed Cu 2? centers is jd z 2[ with a small admixture of jd x 2 Ày 2[ . The rhombic distortions for both Cu 2? centers are obtained from the calculations. The results are discussed.

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“…This crystal is used as host for the studies of interaction between 3d n impurity and host lattice. For example, Ba 2 ZnF 6 is one of the few host crystals in which Cu 2+ can be stabilizedby substitution of Zn 2+ -with a d 2 z ground state [2]. So, various spectroscopic studies were made for Ba 2 ZnF 6 doped with 3d n ions [2 -6].…”

Section: Introductionmentioning

confidence: 99%

A Study of Spin-Hamiltonian Parameters and Defect Structure for Co²⁺ Ion in the Tetragonal Zn²⁺ Site of Ba₂ZnF₆ Crystal

Lia

Zheng

Yang

2010

Zeitschrift Für Naturforschung A

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The spin-Hamiltonian (SH) parameters (g factors g , g ⊥ and hyperfine structure constants A , A ⊥ ) for the Co 2+ ion in the tetragonal Zn 2+ site of a Ba 2 ZnF 6 crystal are calculated from the secondorder perturbation formulas based on the cluster approach for the SH parameters of 3d 7 ions in tetragonal symmetry with the effective spin S = 1/2. In the calculations, a reduction factor due to the dynamical Jahn-Teller effect is used. The calculated results are in reasonable agreement with the experimental values, suggesting that the dynamical Jahn-Teller effect should be considered here. The defect structure of the Co 2+ center in Ba 2 ZnF 6 :Co 2+ is also obtained from the calculations. The results are discussed.

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EPR and ENDOR spectra of copper(II) centers with dz2 and dx2-y2 ground states in barium hexafluorozincate: analysis of hyperfine parameters and dynamic vibronic coupling

Cited by 41 publications

References 2 publications

The Angular Overlap Model and Vibronic Coupling in Treating s-p and d-s Mixing – a DFT Study

The Angular Overlap Model and Vibronic Coupling in Treating s-p and d-s Mixing – a DFT Study

Investigations of EPR g Factors and Rhombic Distortion for the Rhombic Cu2+ Centers in K2Zn1−x Cu x F4 Crystals at Low Temperature

A Study of Spin-Hamiltonian Parameters and Defect Structure for Co²⁺ Ion in the Tetragonal Zn²⁺ Site of Ba₂ZnF₆ Crystal

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EPR and ENDOR spectra of copper(II) centers with dz2 and dx2-y2 ground states in barium hexafluorozincate: analysis of hyperfine parameters and dynamic vibronic coupling

Cited by 41 publications

References 2 publications

The Angular Overlap Model and Vibronic Coupling in Treating s-p and d-s Mixing – a DFT Study

The Angular Overlap Model and Vibronic Coupling in Treating s-p and d-s Mixing – a DFT Study

Investigations of EPR g Factors and Rhombic Distortion for the Rhombic Cu2+ Centers in K2Zn1−x Cu x F4 Crystals at Low Temperature

A Study of Spin-Hamiltonian Parameters and Defect Structure for Co2+ Ion in the Tetragonal Zn2+ Site of Ba2ZnF6 Crystal

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A Study of Spin-Hamiltonian Parameters and Defect Structure for Co²⁺ Ion in the Tetragonal Zn²⁺ Site of Ba₂ZnF₆ Crystal