Absorption spectrum of vanadium(II) chloride from 5000 to 30,000 Cm-1

Kim, Samuel S.; Reed, Stanley A.; Stout, J. W.

doi:10.1021/ic50088a063

Cited by 10 publications

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“…The ampoule was closed in the gas stream and the crystal was grown in the furnace by Stockbarger method at 850 ~ The absorption of our unirradiated crystals in the visible and infrared agrees in principle with that reported by Kuwabara [7]. The spectrum is also qualitatively similar to the published spectra of VC1 z crystals [8,9]. From this fact we conclude that the main amount of vanadium is built-in substitutionally as divalent ion.…”

Section: Methodssupporting

confidence: 88%

Z-like-centers in vanadium doped NaCl crystals

1973

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The absorption, thermostimulated luminescence (TSL) and electron emission (TSE) of prepared and X-irradiated NaCI crystals doped with vanadium were studied. From the TSE-, TSL-and thermo-optical bleaching (TOB-)curves it is suggested that the new 647 nm absorption band and the new TSE-and TSL-peaks at about 480-490 ~ are due to Z-centers, i.e. to the aggregates of F-centers with dipole complexes (divalent vanadium ions and cation vacancies).

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Section: Methodssupporting

confidence: 88%

Z-like-centers in vanadium doped NaCl crystals

1973

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“…1 of 1. c. 18 ). The parameter values calculated by KIM et al 16 are incorrect, since applying eq (1) the fit was based on the estimated energy of the no-phonon transition. No suitable data on the d 3 configuration in tetrahedral environment are known.…”

Section: Resultsmentioning

confidence: 99%

The Nephelauxetic Effect — Calculation and Accuracy of the Interelectronic Repulsion Parameters

König

1972

Zeitschrift Für Naturforschung B

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Expressions are reviewed which may be used to determine 10 Dq and B from the spin-allowed bands in the optical spectra of d 3 and d 7 electron systems within octahedral and tetrahedral sym metry. Application to low-temperature single crystal spectra demonstrates that (i) the semi-empirical ligand field theory reproduces transition energies with sufficient accuracy; (ii) differences in the values of 10 Dq and B observed with different fitting methods may be attributed to the inaccuracy of experimental data; (iii) there are generally valid values of B35 and /?33 for each complex ion.The semi-empirical ligand field theory provides means to completely determine the electronic d -d spectra of transition metal ions of octahedral symmetry in terms of three parameters: the octahedral splitting parameter 10 Dq ( = A) and the interelectronic repulsion parameters (= Racah parameters) B and C which are linear combinations of the Condon-Short ley parameters F2 and1 . An analogous statement applies to tetrahedral symmetry and one or two additional parameters (e. g. Ds and Dt in tetragonal environment) are required if the symmetry is lower than cubic. In general, the numerical values of the parameters B and C, as determined from d -d spectra, are lower than the values in a free transition metal ion. This observation is well known as the nephelauxetic effect 2 ' 3 .In the first part of this study 4 , the author has recently reviewed and tested methods which may be used to determine 10 Dq, B, and C from electronic spectra. To focus the attention on the value of B, these methods were applied to the spin-allowed d -d bands in high-spin d 2 , d 3 , d 7 , and d 8 complexes of octahedral and tetrahedral microsymmetry. In the expressions of the corresponding transition energies, the parameter C does not occur 5 . In addition, 10 Dq may always be fixed by a suitable choice of the calculation method. A convenient check on the accuracy of the employed numerical procedure is provided by calculating the extra band energy, ifRequests for reprints should be sent to Doz. Dr. E. KÖNIG,

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The nephelauxetic effect calculation and accuracy of the interelectronic repulsion parameters I. Cubic high-spin d 2, d 3, d 7, and d 8 systems

König

Structure and Bonding

175

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Absorption spectrum of vanadium(II) chloride from 5000 to 30,000 Cm-1

Cited by 10 publications

References 0 publications

Z-like-centers in vanadium doped NaCl crystals

Z-like-centers in vanadium doped NaCl crystals

The Nephelauxetic Effect — Calculation and Accuracy of the Interelectronic Repulsion Parameters

The nephelauxetic effect calculation and accuracy of the interelectronic repulsion parameters I. Cubic high-spin d 2, d 3, d 7, and d 8 systems

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