Analysis of the Absorption Spectrum of Cesium Uranium (V) Hexafluoride

Reisfeld, Martin J.; Crosby, G. A.

doi:10.1021/ic50023a014

Cited by 86 publications

(28 citation statements)

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“…[19,20] Additionally,w ew ere interested in the absorption spectrum of the highly symmetric [U 2 F 12 ] 2À anion, in which the uranium(V) atoms have the electron configuration [Rn]5f 1 , where on-site f-f electron interaction is absent and thus only afew absorptions can be observed. [19,31,32] This is characteristic for the actinides, Thecalculations for the [U 2 F 12 ] 2À anion were carried out for D 2h symmetry and are in excellent agreement with the recorded spectrum regarding relative intensities and computed energies.U pon comparison of the two calculated anions,t he f-f transitions for the hypothetical [UF 7 ] 2À anion change strongly both in energy and intensity when going to the dinuclear [U 2 F 12 ] 2À anion, showing the effect of f 1 -f 1 pair interactions on the f-f transitions.T hus,f rom the eight possible f-f excitations stemming from the lowest G 5 !…”

supporting

confidence: 58%

The [U₂F₁₂]²⁻ Anion of Sr[U₂F₁₂]

et al. 2018

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The D 2h -symmetric dinuclear complex anion [U 2 F 12 ] 2À of pastel green Sr[U 2 F 12 ]s hows ah itherto unknown structural feature:T he coordination polyhedra around the U atoms are edge-linked monocapped trigonal prisms,t he U V atoms are therefore seven-coordinated. This leads to aU -U distance of 3.8913(6) .Aweak U V -U V interaction is observed for the dinuclear [U 2 F 12 ] 2À complex and described by the antiferromagnetic exchange J exp of circa À29.9 cm À1 .T he crystalline compound can be easily prepared from SrF 2 and b-UF 5 in anhydrous hydrogen fluoride (aHF) at room temperature.I tw as studied by means of single crystal X-ray diffraction, IR, Raman and UV/VIS spectroscopy, magnetic measurements,a nd by molecular as well as by solid-state quantum chemical calculations.

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supporting

confidence: 58%

The [U₂F₁₂]²⁻ Anion of Sr[U₂F₁₂]

et al. 2018

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“…Both the anion and the neutral UF 6 are found to have O h symmetry, in agreement with previous studies. 51 Again, both DFT/PBE and CCSD(T) calculations give similar U-F bond lengths for UF 6 − and UF 6 . The average U−F bond lengths for UF 6 and UF 6 − from CCSD(T) and PBE calculations are 2.10 Å and 2.02 Å, respectively.…”

mentioning

confidence: 80%

“…24,25, Similar to neutral UF 6 , the UF 6 − anion in the Cs + [UF 6 − ] crystal has also been shown to possess the O h symmetry. 51 The ground state of UF 6 − has the neutral UF 6 electronic a) E-mail: junli@mail.tsinghua.edu.cn. b) E-mail: lai-sheng_wang@brown.edu.…”

Section: Introductionmentioning

confidence: 99%

Photoelectron spectroscopy and theoretical studies of UF5− and UF6−

Dau

Su²,

Liu³

et al. 2012

The Journal of Chemical Physics

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The UF(5)(-) and UF(6)(-) anions are produced using electrospray ionization and investigated by photoelectron spectroscopy and relativistic quantum chemistry. An extensive vibrational progression is observed in the spectra of UF(5)(-), indicating significant geometry changes between the anion and neutral ground state. Franck-Condon factor simulations of the observed vibrational progression yield an adiabatic electron detachment energy of 3.82 ± 0.05 eV for UF(5)(-). Relativistic quantum calculations using density functional and ab initio theories are performed on UF(5)(-) and UF(6)(-) and their neutrals. The ground states of UF(5)(-) and UF(5) are found to have C(4v) symmetry, but with a large U-F bond length change. The ground state of UF(5)(-) is a triplet state ((3)B(2)) with the two 5f electrons occupying a 5f(z3)-based 8a(1) highest occupied molecular orbital (HOMO) and the 5f(xyz)-based 2b(2) HOMO-1 orbital. The detachment cross section from the 5f(xyz) orbital is observed to be extremely small and the detachment transition from the 2b(2) orbital is more than ten times weaker than that from the 8a(1) orbital at the photon energies available. The UF(6)(-) anion is found to be octahedral, similar to neutral UF(6) with the extra electron occupying the 5f(xyz)-based a(2u) orbital. Surprisingly, no photoelectron spectrum could be observed for UF(6)(-) due to the extremely low detachment cross section from the 5f(xyz)-based HOMO of UF(6)(-).

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“…Mit Hilfe von G1. Erhebliche Unterschiede zwischen den berechneten Elektroneniibergangen sowie dem berechneten g-Faktor und den experimentellen Werten ergaben sich in [2,6,7,8,9] bei Anwendung der iiblichen Ligandenfeldtheorie. In diesem Modell sind k und k' nicht explizit enthalten.…”

Section: Introductionunclassified

“…Lit.). Die Abweichung der in [2,6,7,8,9] fur die Ligandenfeldparameter angegebenen Werten von den A-und 9-Werten in Tab. 2 der vorliegenden Arbeit ist erheblich.…”

Section: Introductionunclassified

Die konsistente ligandenfeldtheoretische Interpretation des spektroskopischen und magnetischen Verhaltens des 5‐Elektronensystems in oktaedrischen Halogenokomplexen

Eichberger

Lux

1980

Ber Bunsenges Phys Chem

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Auf der Grundlage eines erweiterten ligandenfeldtheoretischen Ansatzes, der auch Kovalenzeffekte erfaßt, wurden f‐f‐Spektren und Magnetismus oktaedrischer [M f 1X6]n‐‐Komplexe (M = Ln, An; X = F, Cl, Br) interpretiert. Zur Bestimmung der in diesem Ansatz auftretenden Parameter (ζ δ, θ, k, k1) wurde ein neues Auswerteverfahren entwickelt. Dadurch ließen sich erstmals sowohl die spektroskopischen wie die magnetischen Eigenschaften der genannten Verbindungen widerspruchsfrei beschreiben. Die ermittelten ζ‐Werte stimmen mit den Spin‐Bahn‐Kopplungskonstanten der entsprechenden freien Ionen überein. Es wird gezeigt, daß man durch Verwendung der Orbitalreduktionsfaktoren k und k1 eine Beeinflussung der Ligandenfeldparameter δ und θ durch Kovalenzeffekte vermeidet. Aus dem Trend der k‐ und k1‐Werte beim Übergang von Fluoro‐ zu Chloro‐ und Bromokomplexen folgt, daß eine Änderung der Kovalenz nur auf die T4‐Orbitale einwirkt.

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Analysis of the Absorption Spectrum of Cesium Uranium (V) Hexafluoride

Cited by 86 publications

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The [U₂F₁₂]²⁻ Anion of Sr[U₂F₁₂]

The [U₂F₁₂]²⁻ Anion of Sr[U₂F₁₂]

Photoelectron spectroscopy and theoretical studies of UF5− and UF6−

Die konsistente ligandenfeldtheoretische Interpretation des spektroskopischen und magnetischen Verhaltens des 5‐Elektronensystems in oktaedrischen Halogenokomplexen

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Analysis of the Absorption Spectrum of Cesium Uranium (V) Hexafluoride

Cited by 86 publications

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The [U2F12]2− Anion of Sr[U2F12]

The [U2F12]2− Anion of Sr[U2F12]

Photoelectron spectroscopy and theoretical studies of UF5− and UF6−

Die konsistente ligandenfeldtheoretische Interpretation des spektroskopischen und magnetischen Verhaltens des 5‐Elektronensystems in oktaedrischen Halogenokomplexen

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The [U₂F₁₂]²⁻ Anion of Sr[U₂F₁₂]

The [U₂F₁₂]²⁻ Anion of Sr[U₂F₁₂]