Characterization of pentavalent and hexavalent americium complexes in nitric acid using X-ray absorption fine structure spectroscopy and first-principles modeling
Abstract
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).
- Authors:
-
- 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)
- Publication Date:
- Research Org.:
- Idaho National Laboratory (INL), Idaho Falls, ID (United States)
- Sponsoring Org.:
- USDOE Office of Nuclear Energy (NE); USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1357492
- Report Number(s):
- INL/JOU-15-36872
Journal ID: ISSN 0236-5731; PII: 4704
- Grant/Contract Number:
- AC07-05ID14517; AC07-99ID13727; AC04-94AL85000
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Radioanalytical and Nuclear Chemistry
- Additional Journal Information:
- Journal Volume: 309; Journal Issue: 3; Journal ID: ISSN 0236-5731
- Publisher:
- Springer
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; Acidic Solution; Americium; Density Functional Theory; Oxidation; X-ray Absorption Fine Structure
Citation Formats
Riddle, Catherine, Czerwinski, Kenneth, Kim, Eunja, Paviet, Patricia, Weck, Philippe, Poineau, Frederic, and Conradson, Steven. Characterization of pentavalent and hexavalent americium complexes in nitric acid using X-ray absorption fine structure spectroscopy and first-principles modeling. United States: N. p., 2016.
Web. doi:10.1007/s10967-016-4704-x.
Riddle, Catherine, Czerwinski, Kenneth, Kim, Eunja, Paviet, Patricia, Weck, Philippe, Poineau, Frederic, & Conradson, Steven. Characterization of pentavalent and hexavalent americium complexes in nitric acid using X-ray absorption fine structure spectroscopy and first-principles modeling. United States. https://doi.org/10.1007/s10967-016-4704-x
Riddle, Catherine, Czerwinski, Kenneth, Kim, Eunja, Paviet, Patricia, Weck, Philippe, Poineau, Frederic, and Conradson, Steven. Mon .
"Characterization of pentavalent and hexavalent americium complexes in nitric acid using X-ray absorption fine structure spectroscopy and first-principles modeling". United States. https://doi.org/10.1007/s10967-016-4704-x. https://www.osti.gov/servlets/purl/1357492.
@article{osti_1357492,
title = {Characterization of pentavalent and hexavalent americium complexes in nitric acid using X-ray absorption fine structure spectroscopy and first-principles modeling},
author = {Riddle, Catherine and Czerwinski, Kenneth and Kim, Eunja and Paviet, Patricia and Weck, Philippe and Poineau, Frederic and Conradson, Steven},
abstractNote = {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).},
doi = {10.1007/s10967-016-4704-x},
journal = {Journal of Radioanalytical and Nuclear Chemistry},
number = 3,
volume = 309,
place = {United States},
year = {Mon Jan 18 00:00:00 EST 2016},
month = {Mon Jan 18 00:00:00 EST 2016}
}
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A general study of actinyl hydration by molecular dynamics simulations using ab initio force fields
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