Infrared matrix study of reactions of UF4 with fluorine

Kunze, Kenneth R.; Hauge, Robert H.; Hamill, D.; Margrave, John L.

doi:10.1063/1.433256

Cited by 18 publications

(11 citation statements)

References 3 publications

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“…Also the infrared spectra of UF 4 were measured by Kunze et al [13,14] and Bukhmarina et al [15][16][17]. They observed a large number of absorption bands in the far-infrared at about 101 cm À1 and the stretching region at about 540 cm À1 .…”

Section: Introductionmentioning

confidence: 98%

“…The uranium tetrahalides play important roles in nuclear fuel enrichment and reprocessing [1], which have been studied in detail both in the solid state [2] and the gas phase [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21]. The first experimental electron diffraction studies of the uranium tetrahalides date from 1958 and were interpreted as regular tetrahedral geometries [3].…”

Section: Introductionmentioning

confidence: 99%

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A relativistic density functional study of gaseous uranium tetrahalides

Zhang¹,

Li²,

Hao³

2008

Molecular Physics

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The molecular structures and vibrational frequencies of gaseous UX 4 (X ¼ F, Cl, Br and I) molecules have been investigated using generalized gradient approximation (GGA) functions (BP, BLYP, PBE and RPBE) with triplezeta polarized (TZP) basis set. Scalar relativistic effects are introduced via the zeroth-order regular approximation (ZORA) approach to the Dirac equation in the present study. Of the methods examined here the RPBE has the best performance in terms of the errors compared with experiment and reference for the vibrational frequencies. The bond dissociation energies (BDE) for U-X bonds in the UX 4 were obtained using the RPBE method, and are in good agreement with experimental values. In addition, satisfactory calculated entropies of UX 4 have also been obtained at temperatures ranging from 600 to 1200 K in 50 steps using the same method.

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Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

A relativistic density functional study of gaseous uranium tetrahalides

Zhang¹,

Li²,

Hao³

2008

Molecular Physics

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“…The 1 F product species was probably formed by a gasphase reaction between F 2 and UC1 4 before the matrix can quench the excess internal energy of UC1 4 which was vaporized at 415-445°C. In the matrix IR study on fluorination of UF 4 [1], both UF 5 and UF 6 were formed during the codeposition. Since the 1 F absorption was unchanged by the photolysis which promotes the addition of two F atoms to UC1 4 , the 1 F product is most likely due to a single F atom addition to UC1 4 , and the 1 /"band has been assigned to the UC1 4 F. The structure of UC1 4 F cannot be determined from the single 1 F absorption.…”

Section: Uci4f Trans-ucl 4 F 2 and Cis-ucl 4 Fmentioning

confidence: 99%

“…Earlier matrix isolation infrared studies [1,2] on the UF 4 reaction with F 2 and Cl 2 have observed several U -F modes for UF 5 , UF 4 C1, and UF 4 C1 2 . Similarly, UF5CI along with excess UF 6 has been isolated in various matrices and characterized using infrared spectroscopy [3].…”

Section: Introductionmentioning

confidence: 96%

“…In addition, the solid inert gas matrices significantly reduce the potential of overlapping absorptions which hampered the IR study [4] on the uranium halides in liquid Xe. Like the earlier studies on the UF 4 reactions [1,2], the purpose of this matrix IR study is to characterize the uranium (V and VI) halides due to halogenation reactions, but this time the fluorination and chlorination have been approached with the UC1 4 reactant. The first IR spectra of UC1 4 F and UCI5 will be described below.…”

Section: Introductionmentioning

confidence: 99%

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Matrix Infrared Study on the Fluorination and Chlorination of UCl₄

1993

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Uranium tetrachloride was condensed with fluorine in excess argon at 12 ± 1 K, and an absorption due to UCI4F was observed at 588.3 cm -1 . Photolysis produced primarily trans-UCl 4 F 2 which has infrared bands at 621.4 and 350.8 cm -1 . Sample annealing, which facilitated F atom addition to UCI4 and UCI4F, dramatically increased the 613.6, 579.2, and 359.3 cm" 1 absorptions due to CÌS-UCI4F2. In contrast, no reaction was detected when UCI4 and chlorine were codeposited; however, photolysis produced a 358.2 cm -1 band which is assigned to UC1 6 . UC1 5 was generated by reacting UCI4 with CI atoms during deposition and identified by an absorption at 351.9 cm -1 .

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Comparative study of relativistic density functional methods applied to actinide species AcO₂²⁺ and AcF₆ for Ac = U, Np

et al. 2002

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A two-component relativistic density functional method based on the Douglas-Kroll-Hess transformation has been applied to the actinyls and hexafluorides of U and Np. All-electron scalar relativistic calculations as well as calculations including spin-orbit interaction have been compared to results obtained with a pseudopotential approach. In addition, several exchange-correlation potentials have been applied to examine their performance for the bond lengths and vibrational frequencies of the title compounds. The calculations confirm the well-known accuracy of the LDA approach for geometries and frequencies, which is corroborated for the hexafluorides where gas phase experimental data are available. Comparison with results of accurate wave function based methods provides further confirmation of this finding. Gradient-corrected functionals tend to overestimate bond lengths and underestimate frequencies also for actinide compounds. The results obtained with Stoll-Preuss (small core) effective core potentials agree very well with those of all-electron calculations, while calculations with Hay-Martin large core pseudopotentials are somewhat less accurate. For all molecules and properties considered, spin-orbit effects have been found negligible concomitant with the closed-shell electronic structure of the U(VI) compounds and the open-shell situation of the Np(VI) compounds with a single valence f electron.

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Infrared matrix study of reactions of UF4 with fluorine

Abstract: Chemical reactions between UF4 and fluorine to produce UF5 and UF6 were studied by the technique of matrix isolation and observation of infrared spectra of reacting species in the matrix.(AIP)

Cited by 18 publications

References 3 publications

A relativistic density functional study of gaseous uranium tetrahalides

A relativistic density functional study of gaseous uranium tetrahalides

Matrix Infrared Study on the Fluorination and Chlorination of UCl₄

Comparative study of relativistic density functional methods applied to actinide species AcO₂²⁺ and AcF₆ for Ac = U, Np

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Infrared matrix study of reactions of UF4 with fluorine

Abstract: Chemical reactions between UF4 and fluorine to produce UF5 and UF6 were studied by the technique of matrix isolation and observation of infrared spectra of reacting species in the matrix.(AIP)

Cited by 18 publications

References 3 publications

A relativistic density functional study of gaseous uranium tetrahalides

A relativistic density functional study of gaseous uranium tetrahalides

Matrix Infrared Study on the Fluorination and Chlorination of UCl4

Comparative study of relativistic density functional methods applied to actinide species AcO22+ and AcF6 for Ac = U, Np

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Matrix Infrared Study on the Fluorination and Chlorination of UCl₄

Comparative study of relativistic density functional methods applied to actinide species AcO₂²⁺ and AcF₆ for Ac = U, Np