Structural study of the ammonium octafluoroneptunate, [NH4]4NpF8

Poineau, Frederic; Silva, Chinthaka M.; Yeamans, Charles B.; Cerefice, Gary S.; Sattelberger, Alfred P.; Czerwinski, Kenneth R.

doi:10.1016/j.ica.2016.04.025

Title: Structural study of the ammonium octafluoroneptunate, [NH₄]₄NpF₈

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Abstract

The [NH₄]₄NpF₈ salt was prepared from the solid-state reaction of NpO₂ with NH₄HF₂ and characterized by powder X-ray diffraction and X-ray absorption fine structure spectroscopy. The diffraction results confirm the compound to be isostructural to [NH₄]₄UF₈ with the following lattice parameter (a = 13.054(4) Å, b = 6.681(2) Å, c = 13.676(5) Å, ß = 121.14 Å). For the first time, a Neptunium fluoride complex has been characterized by XAFS spectroscopy. The energy position of the white line and inflection of the XANES spectra of [NH₄]₄NpF₈ are consistent with the presence of Np(IV). Adjustment of the EXAFS spectra indicates that the coordination number (7.4±1.5) and the average Np-F distance (2.26(1) Å) are consistent with the presence of the NpF8 dodecahedron. The average Np-F distance is ~0.02 Å shorter than the U-F distance in [NH₄]₄UF₈ and is a result of the actinide contraction.

Authors:

Poineau, Frederic ^[1]; Silva, Chinthaka M. ^[2]; Yeamans, Charles B. ^[3]; Cerefice, Gary S. ^[4]; Sattelberger, Alfred P. ^[5]; Czerwinski, Kenneth R. ^[1]

Univ. of Nevada, Las Vegas, NV (United States). Dept. of Chemistry
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Univ. of Nevada, Las Vegas, NV (United States). Dept. of Health Physics
Univ. of Nevada, Las Vegas, NV (United States). Dept. of Chemistry; Argonne National Lab. (ANL), Argonne, IL (United States)

Publication Date:: Thu Apr 21 00:00:00 EDT 2016

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1330088

Alternate Identifier(s):: OSTI ID: 1359174

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Inorganica Chimica Acta

Additional Journal Information:: Journal Volume: 448; Journal Issue: C; Journal ID: ISSN 0020-1693

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; EXAFS; Fluoride; Neptunium

Citation Formats


                    Poineau, Frederic, Silva, Chinthaka M., Yeamans, Charles B., Cerefice, Gary S., Sattelberger, Alfred P., and Czerwinski, Kenneth R. Structural study of the ammonium octafluoroneptunate, [NH4]4NpF8.  United States: N. p., 2016. 
Web.  doi:10.1016/j.ica.2016.04.025.

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                    Poineau, Frederic, Silva, Chinthaka M., Yeamans, Charles B., Cerefice, Gary S., Sattelberger, Alfred P., & Czerwinski, Kenneth R. Structural study of the ammonium octafluoroneptunate, [NH4]4NpF8.  United States.  https://doi.org/10.1016/j.ica.2016.04.025

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                    Poineau, Frederic, Silva, Chinthaka M., Yeamans, Charles B., Cerefice, Gary S., Sattelberger, Alfred P., and Czerwinski, Kenneth R. Thu .  
"Structural study of the ammonium octafluoroneptunate, [NH4]4NpF8".  United States.  https://doi.org/10.1016/j.ica.2016.04.025.  https://www.osti.gov/servlets/purl/1330088.

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@article{osti_1330088,

  title        = {Structural study of the ammonium octafluoroneptunate, [NH4]4NpF8},

  author       = {Poineau, Frederic and Silva, Chinthaka M. and Yeamans, Charles B. and Cerefice, Gary S. and Sattelberger, Alfred P. and Czerwinski, Kenneth R.},

  abstractNote = {The [NH4]4NpF8 salt was prepared from the solid-state reaction of NpO2 with NH4HF2 and characterized by powder X-ray diffraction and X-ray absorption fine structure spectroscopy. The diffraction results confirm the compound to be isostructural to [NH4]4UF8 with the following lattice parameter (a = 13.054(4) Å, b = 6.681(2) Å, c = 13.676(5) Å, ß = 121.14 Å). For the first time, a Neptunium fluoride complex has been characterized by XAFS spectroscopy. The energy position of the white line and inflection of the XANES spectra of [NH4]4NpF8 are consistent with the presence of Np(IV). Adjustment of the EXAFS spectra indicates that the coordination number (7.4±1.5) and the average Np-F distance (2.26(1) Å) are consistent with the presence of the NpF8 dodecahedron. The average Np-F distance is ~0.02 Å shorter than the U-F distance in [NH4]4UF8 and is a result of the actinide contraction.},

  doi          = {10.1016/j.ica.2016.04.025},

  journal      = {Inorganica Chimica Acta},

  number       = C,

  volume       = 448,

  place        = {United States},

  year         = {Thu Apr 21 00:00:00 EDT 2016},

  month        = {Thu Apr 21 00:00:00 EDT 2016}

}

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Title: Structural study of the ammonium octafluoroneptunate, [NH4]4NpF8

Abstract

Citation Formats

Title: Structural study of the ammonium octafluoroneptunate, [NH₄]₄NpF₈