Absorption and magnetic circular dichroism spectra of the compressed copper (II) ion in K2ZnF4

Riley, Mark J.; Dubicki, Lucjan; Moran, Grainne; Krausz, Elmars; Yamada, Isao

doi:10.1016/0301-0104(90)87045-d

Cited by 28 publications

(46 citation statements)

References 22 publications

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“…In particular, the calculations give a value of the tetragonal distortion, u, that is higher for KCuF 3 than that for K 2 CuF 4 , in agreement with experimental data. 24,25 As a salient feature, the present calculations reproduce that the CuF 6 4− complexes are elongated in K 2 CuF 4 , KCuF 3 , and KZnF 3 / Cu 2+15,17,18,24,25 but compressed in K 2 ZnF 4 /Cu 2+ , a fact that is also in agreement with experimental findings 16 and results from ab initio calculations. 31 According to Table 1, the experimental u value for K 2 CuF 4 (28.7 pm) is 16% smaller than that for KCuF 3 (33.3 pm).…”

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confidence: 92%

“…Also, comparing K 2 CuF 4 with KCuF 3 , we observe that the first compound displays a smaller tetragonal distortion than the second one (u is reduced by 16%), but the experimental splitting Δ is surprisingly 8% larger. Moreover, the |Δ| value for K 2 ZnF 4 /Cu 2+ has been measured 16 to be equal to ∼0.7 eV, while it should be below 0.5 eV for KZnF 3 /Cu 2+ according to experimental data. 17 Seeking to clear out these puzzling facts, we have first carried out ab initio periodic calculations in order to determine the equilibrium geometry of the CuF 6 4− complexes in the four insulating lattices.…”

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confidence: 99%

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Compounds Containing Tetragonal Cu²⁺ Complexes: Is the d_x²–y²–d_3z²–r² Gap a Direct Reflection of the Distortion?

García‐Fernández

Barriuso

Garcı́a-Lastra

et al. 2013

J. Phys. Chem. Lett.

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It is widely assumed that the gap, Δ, between d x 2 −y 2 and d 3z 2 −r 2 orbitals in fluorides and oxides containing tetragonal Cu 2+ or Ag 2+ complexes directly reflects the tetragonal distortion in the MX 6 complex (M = d 9 ion; X = F − , O 2− ). This assumption on that relevant quantity is shown to be not correct through the study of pure K 2 CuF 4 -, KCuF 3 -, and Cu 2+ -doped KZnF 3 and K 2 ZnF 4 model compounds. Indeed, ab initio calculations prove that Δ in these insulating materials also depends on the internal electric field created by the rest of lattice ions on active electrons confined in a given CuF 6 4− complex. This internal field, especially important for layered compounds, is shown to explain all puzzling experimental facts on the d−d transitions of the studied systems and is of interest in the search of new Cu 2+ and Ag 2+ superconducting materials where a strong correlation between Δ and the transition temperature, T c , has been conjectured.

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confidence: 92%

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confidence: 99%

Compounds Containing Tetragonal Cu²⁺ Complexes: Is the d_x²–y²–d_3z²–r² Gap a Direct Reflection of the Distortion?

García‐Fernández

Barriuso

Garcı́a-Lastra

et al. 2013

J. Phys. Chem. Lett.

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“…[26][27][28] The present study can be compared to those cases where Cu͑II͒ is doped into a cubic host. This results in Jahn-Teller distorted tetragonally elongated Cu II L 6 species being formed with local D 4h symmetry, and occurs for the cubic KZnF 3 ͑Ref.…”

Section: E MCD Selection Rulesmentioning

confidence: 99%

The highly resolved electronic spectrum of the square planar CuCl42− ion

Dick

Rahemi

Krausz

et al. 2008

The Journal of Chemical Physics

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Articles you may be interested inAbsence of exchange interaction between localized magnetic moments and conduction-electrons in diluted Er3+ gold-nanoparticles J. Appl. Phys. 115, 17E128 (2014) The low temperature magnetic circular dichroism ͑MCD͒ and electron paramagnetic resonance ͑EPR͒ spectra of Cu͑II͒ doped Cs 2 ZrCl 6 are reported. The Cu͑II͒ ion is incorporated as the square planar copper tetrachloride ion, CuCl 4 2− , which substitutes at the Zr͑IV͒ site in the Cs 2 ZrCl 6 lattice, with a complete absence of axial coordination. Both the EPR and MCD show highly resolved spectra from which it is possible to determine the superhyperfine coupling constants and excited state geometries respectively. The Franck-Condon intensity patterns suggest that there is a substantial relaxation of the host lattice about the impurity ion. For the lowest energy 2 B 1g ͑x 2 -y 2 ͒ → 2 B 2g ͑xy͒ transition, both the magnetic dipole allowed electronic origin as well as vibronic false origins are observed. The high resolution of the spectra allowed the accurate determination of the odd parity vibrations that are active in the spectra. The opposite sign of the MCD of the two components of the 2 E g ͑xz , yz͒ excited state allows this splitting to be determined for the first time. Accurate and unambiguous spectral parameters for the CuCl 4 2− ion are important as it has become a benchmark transition metal complex for theoretical electronic structure calculations.

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“…(I) center mentioned above] in K 2 Zn 1-x Cu x F 4 crystals were measured and two zero phonon lines at 7,497 and 8,704 cm -1 assigned, respectively, to C 6 (A 1g jd z 2[ ) ? C 7 (E g ) and C 6 (E g ) transitions were given [27,28]. In the above calculations, if we let the distortion DR = 0, the 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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Absorption and magnetic circular dichroism spectra of the compressed copper (II) ion in K2ZnF4

Cited by 28 publications

References 22 publications

Compounds Containing Tetragonal Cu²⁺ Complexes: Is the d_x²–y²–d_3z²–r² Gap a Direct Reflection of the Distortion?

Compounds Containing Tetragonal Cu²⁺ Complexes: Is the d_x²–y²–d_3z²–r² Gap a Direct Reflection of the Distortion?

The highly resolved electronic spectrum of the square planar CuCl42− ion

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

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Absorption and magnetic circular dichroism spectra of the compressed copper (II) ion in K2ZnF4

Cited by 28 publications

References 22 publications

Compounds Containing Tetragonal Cu2+ Complexes: Is the dx2–y2–d3z2–r2 Gap a Direct Reflection of the Distortion?

Compounds Containing Tetragonal Cu2+ Complexes: Is the dx2–y2–d3z2–r2 Gap a Direct Reflection of the Distortion?

The highly resolved electronic spectrum of the square planar CuCl42− ion

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

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Product

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Compounds Containing Tetragonal Cu²⁺ Complexes: Is the d_x²–y²–d_3z²–r² Gap a Direct Reflection of the Distortion?

Compounds Containing Tetragonal Cu²⁺ Complexes: Is the d_x²–y²–d_3z²–r² Gap a Direct Reflection of the Distortion?