Crystal structure and spectroscopic characterization of cesium vanadium sulfate CsV(SO4)2. Evidence for an electronic Raman transition

Berg, Rolf W.; Boghosian, Soghomon; Bjerrum, Niels; Fehrmann, Rasmus; Krebs, B.; Straeter, N.; Mortensen, O. Sonnich; Papatheodorou, George

doi:10.1021/ic00074a012

Cited by 32 publications

(28 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…In the opinion of the authors, the spectra are second only to those reported for Cu͑II͒ doped CaO, in terms of the information that they provide on the energies and wave functions of the low-lying electronic states of a transition metal ion. Unlike electronic Raman spectra previously reported for other vanadium ͑III͒ species, [28][29][30][31] transitions from the spinor levels of the 3 A ͑C 3 ͒ ground term to those of the 3 E ͑C 3 ͒ term are well resolved. The data have been interpreted in conjunction with results reported from EPR studies, and the conventional ligand field description found wanting.…”

Section: Discussioncontrasting

confidence: 58%

“…[20][21][22][23][24][25][26][27] For a reason not altogether clear, molecular vanadium͑III͒ species are highly amenable to electronic Raman spectroscopy. The 3 A → 3 E͑C 3 ͒ transition has been reported for the vanadium͑III͒ cation coordinated by both water 28,29 and sulphate 30,31 groups, usually manifesting in a broad featureless band. GuVSH crystallizes in the trigonal P31m space group.…”

Section: Introductionmentioning

confidence: 97%

See 1 more Smart Citation

Electronic Raman spectroscopy of the vanadium(III) hexaaqua cation in guanidinium vanadium sulphate: Quintessential manifestation of the dynamical Jahn–Teller effect

Carver

Spichiger²,

Tregenna‐Piggott³

2005

The Journal of Chemical Physics

View full text Add to dashboard Cite

Single-crystal Raman spectra are presented for the salt [C(NH2)3][V(OH2)6](SO4)2, displaying electronic transitions between the trigonal components of the vanadium(III) 3T1g(Oh) ground term. The 3A-->3E(C3) electronic Raman band is centered at approximately 2720 cm-1, and exhibits extensive structure, revealing the energies of the spinor components of the 3E(C3) term for the two crystallographically distinct [V(OH2)6]3+ cations. The data are interpreted in conjunction with parameters previously reported from an electron paramagnetic resonance study of the salt. A satisfactory reproduction of the electronic Raman profile and ground-state spin-Hamiltonian parameters is achieved by employing a (3A plus sign in circle3E)multiply sign in circle e vibronic coupling model, in which the spin-orbit splitting of the 3E(C3) is quenched significantly by the Ham effect, and the intensity of harmonics of the Jahn-Teller active vibration enhanced by their proximity to the electronic Raman bands. The model gives an excellent account of the intensities of the electronic Raman bands, which are shown to depend profoundly on both temperature and the selected component of the polarizability tensor. The electronic Raman profile changes notably upon deuteriation, a result that exposes deficiencies in the single-mode coupling model.

show abstract

Section: Discussioncontrasting

confidence: 58%

Section: Introductionmentioning

confidence: 97%

Electronic Raman spectroscopy of the vanadium(III) hexaaqua cation in guanidinium vanadium sulphate: Quintessential manifestation of the dynamical Jahn–Teller effect

Carver

Spichiger²,

Tregenna‐Piggott³

2005

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…610 A polymeric material with repeating [V III (OH)(SO 4 ) 2 ] 2-units has also been recently obtained (123). 607 Other inorganic V(III) sulfate complexes have been structurally and spectroscopically characterized, [611][612][613][614][615] including the anhydrous V 2 (SO 4 ) 3 salt. 616 While V(II)-compounds are not likely to exist in biology, they are discussed briefly for completeness and for comparison with V(III)-compounds.…”

Section: Vanadium Sulfate Complexesmentioning

confidence: 99%

The Chemistry and Biochemistry of Vanadium and the Biological Activities Exerted by Vanadium Compounds

et al. 2004

View full text Add to dashboard Cite

“…On account of the stoichiometry of reaction 1 (which is assumed to be the only independent stoichiometric process taking place), the number of moles of S 2 O 7 2-and C 2n-in equilibrium (N eq,S 2 O 7 2-and N eq,C 2n-, respectively), may be expressed in terms of n as follows…”

Section: ' Experimental Sectionmentioning

confidence: 99%

Raman Spectroscopic Study of Tungsten(VI) Oxosulfato Complexes in WO₃−K₂S₂O₇−K₂SO₄ Molten Mixtures: Stoichiometry, Vibrational Properties, and Molecular Structure

et al. 2011

View full text Add to dashboard Cite

The dissolution reaction of WO3 in pure molten K2S2O7 and in molten K2S2O7-K2SO4 mixtures is studied under static equilibrium conditions in the XWO3(0) = 0-0.33 mol fraction range at temperatures up to 860 °C. High temperature Raman spectroscopy shows that the dissolution leads to formation of W(VI) oxosulfato complexes, and the spectral features are adequate for inferring the structural and vibrational properties of the complexes formed. The band characteristics observed in the W=O stretching region (band wavenumbers, intensities, and polarization characteristics) are consistent with a dioxo W(=O)2 configuration as a core unit within the oxosulfato complexes formed. A quantitative exploitation of the relative Raman intensities in the binary WO3-K2S2O7 system allows the determination of the stoichiometric coefficient, n, of the complex formation reaction WO3 + nS2O7(2-) --> C(2n-). It is found that n = 1; therefore, the reaction WO3 + S2O7(2-) > WO2(SO4)2(2-) with six-fold W coordination is proposed as fully consistent with the observed Raman features. The effects of the incremental dissolution and presence of K2SO4 in WO3-K2S2O7 melts point to a WO3 · K2S2O7 · K2SO4 stoichiometry and a corresponding complex formation reaction in the ternary molten WO3-K2S2O7-K2SO4 system according to WO3 + S2O7(2-) + SO4(2-) --> WO2(SO4)3(4-). The coordination sphere of W in WO2(SO4)2(2-) (binary system) is completed with two oxide ligands and two chelating sulfate groups. A dimeric [{WO2(SO4)2}2(μ-SO4)2](8-) configuration is proposed for the W oxosulfato complex in the ternary system, generated from inversion symmetry of aWO2(SO4)3(4-) moiety resulting in two bridging sulfates. The most characteristic Raman bands for the W(VI) oxosulfato complexes pertain to W(=O)2 stretching modes (i) at 972 (polarized) and 937 (depolarized) cm(-1) for the ν(s) and ν(as) W(=O)2 modes of WO2(SO4)2(2-), and (ii) at 933 (polarized) and 909 (depolarized) cm(-1) for the respective modes of [{WO2(SO4)2}2(μ-SO4)2](8-).

show abstract

Crystal structure and spectroscopic characterization of cesium vanadium sulfate CsV(SO4)2. Evidence for an electronic Raman transition

Cited by 32 publications

References 0 publications

Electronic Raman spectroscopy of the vanadium(III) hexaaqua cation in guanidinium vanadium sulphate: Quintessential manifestation of the dynamical Jahn–Teller effect

Electronic Raman spectroscopy of the vanadium(III) hexaaqua cation in guanidinium vanadium sulphate: Quintessential manifestation of the dynamical Jahn–Teller effect

The Chemistry and Biochemistry of Vanadium and the Biological Activities Exerted by Vanadium Compounds

Raman Spectroscopic Study of Tungsten(VI) Oxosulfato Complexes in WO₃−K₂S₂O₇−K₂SO₄ Molten Mixtures: Stoichiometry, Vibrational Properties, and Molecular Structure

Contact Info

Product

Resources

About

Crystal structure and spectroscopic characterization of cesium vanadium sulfate CsV(SO4)2. Evidence for an electronic Raman transition

Cited by 32 publications

References 0 publications

Electronic Raman spectroscopy of the vanadium(III) hexaaqua cation in guanidinium vanadium sulphate: Quintessential manifestation of the dynamical Jahn–Teller effect

Electronic Raman spectroscopy of the vanadium(III) hexaaqua cation in guanidinium vanadium sulphate: Quintessential manifestation of the dynamical Jahn–Teller effect

The Chemistry and Biochemistry of Vanadium and the Biological Activities Exerted by Vanadium Compounds

Raman Spectroscopic Study of Tungsten(VI) Oxosulfato Complexes in WO3−K2S2O7−K2SO4 Molten Mixtures: Stoichiometry, Vibrational Properties, and Molecular Structure

Contact Info

Product

Resources

About

Raman Spectroscopic Study of Tungsten(VI) Oxosulfato Complexes in WO₃−K₂S₂O₇−K₂SO₄ Molten Mixtures: Stoichiometry, Vibrational Properties, and Molecular Structure