Elucidation of the Structure and Vibrational Spectroscopy of Synthetic Metaschoepite and Its Dehydration Product
Abstract
We confirm that synthetic uranyl hydroxide hydrate metaschoepite [(UO)24O(OH)6]·5H2O is unstable against dehydration under dry conditions, and we present a structural and vibrational spectroscopic study of synthetic metaschoepite and its ambient temperature dehydration product. Complementary structural (X-ray diffraction and neutron diffraction) and vibrational spectroscopic techniques (Raman spectroscopy, infrared spectroscopy, and inelastic neutron scattering) are used to probe different components of these species. Analysis of the dehydration product suggests that it contains both pentagonally coordinated and hexagonally coordinated uranyl ions, necessitating that some uranyl ions undergo a coordination change during the dehydration of pentagonally coordinated metaschoepite. Vibrational spectra of metaschoepite and its dehydration product are interpreted with power spectra generated from ab initio molecular dynamics trajectories, allowing assignment of all major features. We identify the uranyl symmetric stretching modes of the four distinct uranyl ions in synthetic metaschoepite and clarify the assignment of lower energy Raman modes in both structures. Finally, the coanalysis of experimental and computational data reveals a strong coupling between the uranyl stretching modes and hydroxide bending modes in the anhydrous structure, leading to the presence of several high-energy combination bands in the inelastic neutron scattering data.
- Authors:
-
[2];
[2];
[2];
[1]
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1720254
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 58; Journal Issue: 11; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; anions; power; cations; dehydration; ions
Citation Formats
Kirkegaard, Marie, Niedziela, Jennifer L., Miskowiec, Andrew J., Shields, Ashley E., and Anderson, Brian. Elucidation of the Structure and Vibrational Spectroscopy of Synthetic Metaschoepite and Its Dehydration Product. United States: N. p., 2019.
Web. doi:10.1021/acs.inorgchem.9b00460.
Kirkegaard, Marie, Niedziela, Jennifer L., Miskowiec, Andrew J., Shields, Ashley E., & Anderson, Brian. Elucidation of the Structure and Vibrational Spectroscopy of Synthetic Metaschoepite and Its Dehydration Product. United States. https://doi.org/10.1021/acs.inorgchem.9b00460
Kirkegaard, Marie, Niedziela, Jennifer L., Miskowiec, Andrew J., Shields, Ashley E., and Anderson, Brian. Fri .
"Elucidation of the Structure and Vibrational Spectroscopy of Synthetic Metaschoepite and Its Dehydration Product". United States. https://doi.org/10.1021/acs.inorgchem.9b00460. https://www.osti.gov/servlets/purl/1720254.
@article{osti_1720254,
title = {Elucidation of the Structure and Vibrational Spectroscopy of Synthetic Metaschoepite and Its Dehydration Product},
author = {Kirkegaard, Marie and Niedziela, Jennifer L. and Miskowiec, Andrew J. and Shields, Ashley E. and Anderson, Brian},
abstractNote = {We confirm that synthetic uranyl hydroxide hydrate metaschoepite [(UO)24O(OH)6]·5H2O is unstable against dehydration under dry conditions, and we present a structural and vibrational spectroscopic study of synthetic metaschoepite and its ambient temperature dehydration product. Complementary structural (X-ray diffraction and neutron diffraction) and vibrational spectroscopic techniques (Raman spectroscopy, infrared spectroscopy, and inelastic neutron scattering) are used to probe different components of these species. Analysis of the dehydration product suggests that it contains both pentagonally coordinated and hexagonally coordinated uranyl ions, necessitating that some uranyl ions undergo a coordination change during the dehydration of pentagonally coordinated metaschoepite. Vibrational spectra of metaschoepite and its dehydration product are interpreted with power spectra generated from ab initio molecular dynamics trajectories, allowing assignment of all major features. We identify the uranyl symmetric stretching modes of the four distinct uranyl ions in synthetic metaschoepite and clarify the assignment of lower energy Raman modes in both structures. Finally, the coanalysis of experimental and computational data reveals a strong coupling between the uranyl stretching modes and hydroxide bending modes in the anhydrous structure, leading to the presence of several high-energy combination bands in the inelastic neutron scattering data.},
doi = {10.1021/acs.inorgchem.9b00460},
journal = {Inorganic Chemistry},
number = 11,
volume = 58,
place = {United States},
year = {Fri May 17 00:00:00 EDT 2019},
month = {Fri May 17 00:00:00 EDT 2019}
}
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