Spectral properties of bis(tetraethylammonium) uranium hexaiodide bis(tetraethylammonium) uranium hexafluoride

Wagner, W.-D.; Edelstein, N.; Whittaker, B.; Brown, David

doi:10.1021/ic50171a010

Cited by 27 publications

(17 citation statements)

References 3 publications

(5 reference statements)

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“…All levels shift to higher energies in Cs 2 GeF 6 , but the shift is not uniform, so that noticeable changes of order are observed going from Cs 2 ZrCl 6 to Cs 2 GeF 6 . All these results agree with available experimental studies that compare hexafluoro and hexachloro complexes of tetravalent uranium in solid salts and in solution, 8,9 as we comment next.…”

Section: B Comparison Of the 5f 2 Manifolds Of Cs 2 Zrcl 6 :U 4+ Andsupporting

confidence: 89%

“…III B, where previous theoretical and experimental results on ͑UX 6 ͒ 2− ͑X =F,Cl͒ are also used. 8,9 The green-to-blue up-conversion luminescence, observed in Cs 2 ZrCl 6 :U 4+ , 38,39 is predicted to be quenched in the fluoride host, as described in Sec. III C. And finally, the results of the high-symmetry model Cs 2 GeF 6 :U 4+ are used in Sec.…”

Section: Resultsmentioning

confidence: 95%

“…As a result, few transitions in the roomtemperature spectra of the ͑AnF 6 ͒ 2− could be unambigously matched to corresponding transitions in the ͑AnCl 6 ͒ 2− , 8 and a detailed analysis of the 5f 2 → 5f 2 transitions was not possible. 8 A comparative study of the low-temperature absorption spectra of ͓͑C 2 H 5 ͒ 4 N͔ 2 UX 6 ͑X =F,Cl,Br,I͒ and of Cs 2 UCl 6 was reported by Wagner et al 9 a few years later. The authors concluded that the spectrum of the ͓͑C 2 H 5 ͒ 4 N͔ 2 UF 6 shows almost no similarity to the other ͑UX͒ 6 2− and that the peaks are strongly shifted to higher energies.…”

Section: B Comparison Of the 5f 2 Manifolds Of Cs 2 Zrcl 6 :U 4+ Andmentioning

confidence: 90%

“…[5][6][7] They are also known to induce stronger electrostatic field than chlorides and bromides which definitely affects the structure of the 5f 1 6d 1 manifold and also of the 5f 2 manifold. 8,9 Vibrational frequencies of fluoride complexes are much higher due to the fluorine small mass, which favors nonradiative decay. Furthermore, it has been recently shown that different combinations of these features, through the choice of different fluoride hosts, may result in strong and fast 5f 1 6d 1 → 5f 2 emission, such as in LiYF 4 :U 4+ , 1,3 or slow 5f 2 → 5f 2 luminescence, such as in YF 3 :U 4+ .…”

Section: Introductionmentioning

confidence: 99%

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5 f → 5 f transitions of U4+ ions in high-field, octahedral fluoride coordination: The Cs2GeF6:U4+ crystal

Ordejón

Seijo

Barandiarán

2005

The Journal of Chemical Physics

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The U-F bond length, totally symmetric vibrational frequency, and 5f 2 energy levels of the Cs 2 GeF 6 :U 4+ crystal are predicted through quantum-chemical calculations on the embedded ͑UF 6 ͒ 2− cluster. The U 4+ ions substitute for much smaller Ge 4+ retaining octahedral site symmetry, which is useful to interpret the electronic transitions. The structure of the 5f 2 manifold: its energy range, the crystal splitting of the 5f 2 levels, their parentage with free-ion levels, and the energy gaps appearing within the manifold, is presented and discussed, which allows to suggest which are the possible 5f 2 luminescent levels. The effects of Cl-to-F chemical substitution are discussed by comparison with isostructural Cs 2 ZrCl 6 :U 4+ . The energy range of the 5f 2 manifold increases by some 6000 cm −1 and all levels shift to higher energies, but the shift is not uniform, so that noticeable changes of order are observed from Cs 2 ZrCl 6 :U 4+ to Cs 2 GeF 6 :U 4+ . The comparison also reveals that the green-to-blue up-conversion luminescence, which has been experimentally detected and theoretically discussed on Cs 2 ZrCl 6 :U 4+ , is quenched in the fluoride host. The results of the Cs 2 GeF 6 :U 4+ are used as a high-symmetry model to try to understand why efficient radiative cascade emissions in the visible do not occur for charged U 4+ defects in low-symmetry YF 3 crystals. The results presented here suggest that theoretical and experimental investigations of 4f /5f ions doped in octahedral, high-symmetry fluoride crystals may be conducted even when the mismatch of ionic radii between the lanthanide/actinide ions and the substituted cations of the host is considerably large. Investigations of these new materials should reveal interesting spectroscopic features without the difficulties associated with more commonly used low-symmetry fluoride hosts.

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Section: B Comparison Of the 5f 2 Manifolds Of Cs 2 Zrcl 6 :U 4+ Andsupporting

confidence: 89%

Section: Resultsmentioning

confidence: 95%

Section: B Comparison Of the 5f 2 Manifolds Of Cs 2 Zrcl 6 :U 4+ Andmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

5 f → 5 f transitions of U4+ ions in high-field, octahedral fluoride coordination: The Cs2GeF6:U4+ crystal

Ordejón

Seijo

Barandiarán

2005

The Journal of Chemical Physics

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“…[14] As the CF strengths of I Ϫ and THF are relatively small, [15] we concluded that this holds also for the Tp Me 2 ligand. Applying method B, the large global CF strengths found for [Ln(COT)(Tp Me 2)] (Ln ϭ Pr, Nd, Sm) [16Ϫ19] were considered to be approximately equal to the individual CF strength of the COT ligand.…”

Section: Introductionmentioning

confidence: 61%

Crystal Field Strengths, Nephelauxetic Effects, and Experimentally Based Molecular Orbital Schemes (in the f Range) of Selected Cyclopentadienyl Complexes of Samarium(III)

et al. 2003

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The absorption and luminescence spectra of pseudo (ψ) trigonal planar [Sm(η5‐C5H4tBu)3] (1), low symmetric [Sm(η5‐Cp)(η3‐Tp)(η2‐Tp)] (Cp = η5‐cyclopentadienyl; Tp = hydrotris(3,5‐dimethylpyrazolyl)borato) (2) as well as ψ trigonal pyramidal [Sm(η5‐C5H4tBu)3(THF)] (3), [Sm(η5‐Cp)3(THF)] (4) and [Sm(η5‐Cp)3(CNC6H11)] (5) have been measured at room and low temperatures. From the spectra obtained, truncated crystal field (CF) splitting patterns of these compounds could be derived, and simulated by fitting the parameters of a phenomenological Hamiltonian. On the basis of the CF parameters used, the global CF strengths experienced by the Sm3+ central ions of complexes 1−5, as well as the individual CF strength associated with one C5H4tBu− ligand are estimated. The obtained Slater parameters F2 and the spin‐orbit coupling parameters ζ4f allow the insertion of compounds 1−5 into truncated nephelauxetic and relativistic nephelauxetic series. Besides, the experimentally based non‐relativistic and relativistic molecular orbital schemes (in the f range) of complexes 1 and, partly, 3 are set up and compared with the results of quantum chemical model calculations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Computational Tools for Predictive Modeling of Properties in Complex Actinide Systems

Autschbach¹,

Govind²,

Atta‐Fynn³

et al. 2015

Computational Methods in Lanthanide and Actinide Chemistry

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Spectral properties of bis(tetraethylammonium) uranium hexaiodide bis(tetraethylammonium) uranium hexafluoride

Cited by 27 publications

References 3 publications

5 f → 5 f transitions of U4+ ions in high-field, octahedral fluoride coordination: The Cs2GeF6:U4+ crystal

5 f → 5 f transitions of U4+ ions in high-field, octahedral fluoride coordination: The Cs2GeF6:U4+ crystal

Crystal Field Strengths, Nephelauxetic Effects, and Experimentally Based Molecular Orbital Schemes (in the f Range) of Selected Cyclopentadienyl Complexes of Samarium(III)

Computational Tools for Predictive Modeling of Properties in Complex Actinide Systems

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