Characterization of pentavalent and hexavalent americium complexes in nitric acid using X-ray absorption fine structure spectroscopy and first-principles modeling

Riddle, Catherine; Czerwinski, Kenneth; Kim, Eunja; Paviet, Patricia; Weck, Philippe; Poineau, Frederic; Conradson, Steven

doi:10.1007/s10967-016-4704-x

Title: Characterization of pentavalent and hexavalent americium complexes in nitric acid using X-ray absorption fine structure spectroscopy and first-principles modeling

Journal Article · Mon Jan 18 00:00:00 EST 2016 · Journal of Radioanalytical and Nuclear Chemistry

DOI:https://doi.org/10.1007/s10967-016-4704-x· OSTI ID:1357492

Riddle, Catherine ^[1]; Czerwinski, Kenneth ^[2]; Kim, Eunja ^[3]; Paviet, Patricia ^[4]; Weck, Philippe ^[5]; Poineau, Frederic ^[2]; Conradson, Steven ^[6]

Idaho National Lab. (INL), Idaho Falls, ID (United States)
Univ. of Nevada, Las Vegas, NV (United States). Dept. of Chemistry
Univ. of Nevada, Las Vegas, NV (United States). Dept. of Physics and Astronomy
Dept. of Energy (DOE), Washington, DC (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Soleil, Paris (France)

We studied the speciation of pentavalent and hexavalent americium (Am) complexes in nitric acidicby X-ray absorption fine structure spectroscopy (XAFS), UV-visible spectroscopy, and density functional theory (DFT). Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) results were consistent with the presence of a mixture of AmO₂⁺ and AmO₂²⁺ with only a small amount AmO₂ present. The resulting average bond distances we found were 1.71 Å for Am=O and 2.44 Å for Am-O. All-electron scalar relativistic calculations were also carried out using DFT to predict the equilibrium geometries and properties of the AmO₂⁺ and AmO₂²⁺ aquo complexes. Calculated bond distances for the Am(VI) complex are in reasonable agreement with EXAFS data and the computed energy gaps between frontier molecular orbitals suggest a slightly higher kinetic stability and chemical hardness of Am(VI) compared to Am(V).

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Research Organization:: Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC07-05ID14517; AC07-99ID13727; AC04-94AL85000

OSTI ID:: 1357492

Report Number(s):: INL/JOU-15-36872; PII: 4704

Journal Information:: Journal of Radioanalytical and Nuclear Chemistry, Vol. 309, Issue 3; ISSN 0236-5731

Publisher:: SpringerCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 7 works

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38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
Acidic Solution
Americium
Density Functional Theory
Oxidation
X-ray Absorption Fine Structure

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