Preparation of cubic chloro complex compounds of trivalent metals: Cs2NaMCl6

Morss, Lester R.; Siegal, Michael P.; Stenger, L.; Edelstein, Norman M.

doi:10.1021/ic50089a034

Cited by 352 publications

(172 citation statements)

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(3 reference statements)

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“…Trivalent lanthanide ions Ln 3+ doped in Cs 2 NaYCl 6 substitute for some of the Y 3+ ions in the sites of exact octahedral ͑O h ͒ symmetry, where they are surrounded by a first coordination shell of six Cl − anions, 28 whose positions become directly affected by the presence of the lanthanide impurities. The electronic states of interest in this work are localized in the vicinities of the Ln 3+ impurities ͑Ln= Ce to Tb͒ and are expected to be well described with wave functions of ͑LnCl 6 ͒ 3− -embedded clusters.…”

Section: Methods and Details Of The Calculationsmentioning

confidence: 99%

Quantum chemical study of 4f→5d excitations of trivalent lanthanide ions doped in the cubic elpasolite Cs2NaYCl6. Ce3+ to Tb3+

Ruipérez

Barandiarán

Seijo

2005

The Journal of Chemical Physics

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Wave-function-based ab initio calculations on the lowest states of the 4f n ,4f n−1 5d͑t 2g ͒ 1 , and 4f n−1 5d͑e g ͒ 1 configurations of ͑LnCl 6 ͒ 3− clusters ͑Ln= Ce to Tb͒ embedded in the cubic elpasolite Cs 2 NaYCl 6 have been performed, in an attempt to contribute to a comprehensive understanding of the 4f → 5d excitations of lanthanide ions in crystals. Reliable data are provided on the changes of bond lengths and breathing mode vibrational frequencies upon 4f → 5d͑t 2g ͒ and 4f → 5d͑e g ͒ excitations, as well as on minimum-to-minimum and vertical absorption and emission transitions, and on the Stokes shifts. The available experimental data are discussed and predictions are made. The stabilization of the 4f → 5d͑baricenter͒ excitation of the doped ions with respect to the 4f → 5d excitations of the free ions, which is a key variable for the understanding of these excitations in solid hosts, is analyzed and found to be due, in two-thirds, to dynamic ligand correlation effects and, in one-third, to orbital relaxation, charge transfer, and covalency effects present in a mean-field approximation.

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Section: Methods and Details Of The Calculationsmentioning

confidence: 99%

Quantum chemical study of 4f→5d excitations of trivalent lanthanide ions doped in the cubic elpasolite Cs2NaYCl6. Ce3+ to Tb3+

Ruipérez

Barandiarán

Seijo

2005

The Journal of Chemical Physics

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“…Morss method E. 22 The powders were passed through a Bridgman furnace at ca. 850 o C in vacuo in quartz tubes to give polycrystalline materials.…”

Section: Methodsmentioning

confidence: 99%

Absorption and Emission Spectra of Ce³⁺ in Elpasolite Lattices

et al. 2003

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The experimental determination of the electronic energy levels for Ce 3+ in some chloro-elpasolite hosts for both the ground 4f 1 and the excited 5d 1 configurations are described. High resolution f -f absorption and f -2 T 2g d absorption and emission spectra have been recorded at low temperatures for Ce 3+ diluted into various hexachloroelpasolite lattices. A fluorescence spectrum at ~ 50,000 cm -1 is tentatively assigned to the emission from the highest 5d crystal field level , 2 E g , of a Ce 3+ impurity in Cs 2 NaErCl 6 , enabling the values of all the energy levels of both the 4f 1 and 5d 1 configurations to be given for 2 Ce 3+ in elpasolite hosts. Vibronic structure superimposed on the electronic transitions is analyzed in terms of a simple configurational coordinate model involving the ground and excited configurations. It is found that the difference in the Ce-Cl bondlength between the 4f 1 and 5d 1 configurations is ~0.04Å. Ab initio model potential calculations on the (CeCl 6 ) 3-cluster embedded in a reliable representation of the Cs 2 NaYCl 6 host support these conclusions. IntroductionAt the beginning of the 4f and the 5f transition series, the f and d electronic configurations of the di-, tri-, and tetravalent free ions are very close in energy. 1,2 This is also true for these ions in compounds. For example, the lowest energy configuration for the Ce 2+ free ion is [Xe core]4f 2 with the beginning of the opposite parity 4f5d configuration at 3277 cm -1 . However in a CaF 2 host the ground configuration is [Xe core]4f5d. 3 The Ce 3+ free ion has a 4f 1 ground configuration with the lowest 5d state at 49737 cm -1 . 1 When this ion is placed in a crystal the lowest 4f to 5d electric dipole allowed transition has been reported to be in the range of 20,000 to 40,000 cm -1 depending on the particular compound or matrix investigated. 4 Similarly, for the actinide or 5f series, the lowest 5f -6d transition for the Pa 4+ ion diluted in Cs 2 ZrCl 6 is at 20,000 cm -1 , but the free ion separation between ground 5f level and the first 6d level is ~ 50,000 cm -1 . 5 In the few structurally characterized Th 3+ organometallic compounds the 6d 1 configuration has been found to be the ground configuration, 6,7 but the ground term is from the 5f configuration and the first 6d level is 10,000 cm -1 higher in the Th 3+ free ion.The U 3+ ion in the LaCl 3 host has the first 5f 3 to 5f 2 6d 1 transition at approximately 22,000 cm -1 although in the U 3+ /RbY 2 Cl 7 system this transition is found at ~ 14,000 cm -1 . 8 Thus, as the degree of ionization increases and/or the atomic number is increased (for both the lanthanide and the actinide series) the f n configuration becomes increasingly stabilized so that the interconfigurational transitions are not observed in the visible or near ultraviolet region. Only at the beginning of both the lanthanide and actinide series is it possible to observe these two electronic configurations in this energy range. 3For the lanthanide series the Ce 3+ ion has been extensivel...

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“…Previous values for end members at room temperature of the composition Cs 2 NaY x Ho 1Àx Cl 6 were reported as 10.7315(15) A (Morss et al 1970) for Cs 2 NaYCl 6 and as 10.726 A (Amberger et al, 1976) and 10.72 9 A (sic) (Meyer, Linzmeier, 1977) for Cs 2 NaHoCl 6 . The current work gives values of 10.7275(2) A and 10.7220(2) A, respectively.…”

Section: Structure Of Elpasolitementioning

confidence: 90%

“…Samples of Cs 2 NaY x Ho 1Àx Cl 6 were prepared according to the Bridgman technique (Morss et al, 1970). The reagents, CsCl, NaCl (BDH), and 99.99 per cent purity Ho 2 O 3 and Y 2 O 3 (Berkshire Ores), with 'Aristar' grade concentrated hydrochloric acid, sufficient for a calculated 6 mmol of sample, were heated until the product began to deposit when the hot plate was switched off and the beaker shielded partially from the heat in order to avoid the formation of the oxychloride.…”

Section: Experimental Preparation and Sample Handlingmentioning

confidence: 99%

“…The series of salts, Cs 2 NaMCl 6 , M ¼ Y, LaÀGd, Dy, Er, Tm, Lu (Morss, Siegal, Stengler, and Edelstein, 1970) and Ln ¼ Tb, Ho, Yb (Amberger, Fischer, Rosenbauer, 1976;Meyer, Linzmeier, 1977), was investigated at room temperature by PXRD. The 1970 study reported that the X-ray powder patterns of all compounds investigated could be indexed on the basis of a fcc lattice and the intensities observed were consistent with space group Fm 3 3m with heavy atoms on special positions (e.g.…”

Section: Introduction Crystallographic Backgroundmentioning

confidence: 99%

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A detailed study of the variation in lattice parameter and structure with temperature and dilution in yttrium-substituted holmium hexachloro-elpasolite Cs₂NaY _x Ho_1–xCl₆

Sabry-Grant¹,

Vickers²,

Cockcroft³

2007

Zeitschrift Für Kristallographie

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The lattice parameters of Cs2NaHoCl6 at 25 K, 120 K, and 294 K determined in this work are 10.6389(3) Å, 10.6666(2) Å, and 10.7220(2) Å, respectively, and those of Cs2NaYCl6 at 120 K and 294 K are 10.6722(2) Å and 10.7275(2) Å, respectively, by Rietveld refinement using space group Fm-3m. The variation in structure of Cs2NaY x Ho1−x Cl6 with yttrium substitution for x = 0 to 1 at 120 K and 294 K has been determined. Given the highly-absorbing samples examined by PXRD, great care is needed with the alignment of the diffractometer and the inclusion of suitable corrections in the Rietveld refinement model. The variation of the lattice parameter of Cs2NaHoCl6 with temperature between 100 K and 475 K has been determined. The mean value for the effective, coordination-number-6, ionic radius of trivalent yttrium/holmium in this elpasolite structure at 120 K determined in this work is 0.764(2) Å and at 294 K is 0.766(3) Å, i.e. no change within experimental limits was observed in this value, assuming cubic close-packing of Cl− and Cs+ ions. No long-range ordering was found in the 50 : 50 mixture consistent with random substitution of holmium by yttrium for all compositions. The process is charge-driven as trivalent yttrium replaces the corresponding holmium without displacing monovalent sodium. Thermoluminescence is observed from samples irradiated at low temperature during their return to room temperature.

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Preparation of cubic chloro complex compounds of trivalent metals: Cs2NaMCl6

Cited by 352 publications

References 3 publications

Quantum chemical study of 4f→5d excitations of trivalent lanthanide ions doped in the cubic elpasolite Cs2NaYCl6. Ce3+ to Tb3+

Quantum chemical study of 4f→5d excitations of trivalent lanthanide ions doped in the cubic elpasolite Cs2NaYCl6. Ce3+ to Tb3+

Absorption and Emission Spectra of Ce³⁺ in Elpasolite Lattices

A detailed study of the variation in lattice parameter and structure with temperature and dilution in yttrium-substituted holmium hexachloro-elpasolite Cs₂NaY _x Ho_1–xCl₆

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Preparation of cubic chloro complex compounds of trivalent metals: Cs2NaMCl6

Cited by 352 publications

References 3 publications

Quantum chemical study of 4f→5d excitations of trivalent lanthanide ions doped in the cubic elpasolite Cs2NaYCl6. Ce3+ to Tb3+

Quantum chemical study of 4f→5d excitations of trivalent lanthanide ions doped in the cubic elpasolite Cs2NaYCl6. Ce3+ to Tb3+

Absorption and Emission Spectra of Ce3+ in Elpasolite Lattices

A detailed study of the variation in lattice parameter and structure with temperature and dilution in yttrium-substituted holmium hexachloro-elpasolite Cs2NaY x Ho1–x Cl6

Contact Info

Product

Resources

About

Absorption and Emission Spectra of Ce³⁺ in Elpasolite Lattices

A detailed study of the variation in lattice parameter and structure with temperature and dilution in yttrium-substituted holmium hexachloro-elpasolite Cs₂NaY _x Ho_1–xCl₆