Periodic Trends within Actinyl(VI) Nitrates and Their Structures, Vibrational Spectra, and Electronic Properties
Abstract
In this work, a series of actinyl(VI) nitrate salts of the form MAnO2(NO3)3, where M = NH4+ K+, Rb+, Cs+, and Me4N+ and AnO22+ = U, Np, Pu, and AnO2(NO3)2(H2O)2·H2O, and the uranyl tetranitrates M2UO2(NO3)4 have been synthesized from aqueous solution and their structures determined using single-crystal X-ray diffraction. Together, these complexes represent an isostructural series of actinide complexes among the salts crystallized with the same charge-compensating cation and have been studied using vibrational spectroscopy including Raman and Fourier-transform infrared. Periodic trends in both the structural properties of these complexes and their vibrational spectra are presented and discussed, in particular the invariant nature of the O≡An≡O asymmetric stretching frequencies observed across the actinyl series. Electronic structure calculations were performed at a variety of levels of theory to aid in the interpretation of the vibrational data and to correlate trends in the data with the underlying electronic properties of these molecules.
- Authors:
-
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Univ. of Alabama, Tuscaloosa, AL (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
- OSTI Identifier:
- 1968737
- Grant/Contract Number:
- AC02-06CH11357; SC0018921
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 61; Journal Issue: 39; 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; Cations; Infrared spectroscopy; Ions; Organic polymers
Citation Formats
Autillo, Matthieu, Wilson, Richard E., Vasiliu, Monica, de Melo, Gabriel F., and Dixon, David A. Periodic Trends within Actinyl(VI) Nitrates and Their Structures, Vibrational Spectra, and Electronic Properties. United States: N. p., 2022.
Web. doi:10.1021/acs.inorgchem.2c02434.
Autillo, Matthieu, Wilson, Richard E., Vasiliu, Monica, de Melo, Gabriel F., & Dixon, David A. Periodic Trends within Actinyl(VI) Nitrates and Their Structures, Vibrational Spectra, and Electronic Properties. United States. https://doi.org/10.1021/acs.inorgchem.2c02434
Autillo, Matthieu, Wilson, Richard E., Vasiliu, Monica, de Melo, Gabriel F., and Dixon, David A. Wed .
"Periodic Trends within Actinyl(VI) Nitrates and Their Structures, Vibrational Spectra, and Electronic Properties". United States. https://doi.org/10.1021/acs.inorgchem.2c02434. https://www.osti.gov/servlets/purl/1968737.
@article{osti_1968737,
title = {Periodic Trends within Actinyl(VI) Nitrates and Their Structures, Vibrational Spectra, and Electronic Properties},
author = {Autillo, Matthieu and Wilson, Richard E. and Vasiliu, Monica and de Melo, Gabriel F. and Dixon, David A.},
abstractNote = {In this work, a series of actinyl(VI) nitrate salts of the form MAnO2(NO3)3, where M = NH4+ K+, Rb+, Cs+, and Me4N+ and AnO22+ = U, Np, Pu, and AnO2(NO3)2(H2O)2·H2O, and the uranyl tetranitrates M2UO2(NO3)4 have been synthesized from aqueous solution and their structures determined using single-crystal X-ray diffraction. Together, these complexes represent an isostructural series of actinide complexes among the salts crystallized with the same charge-compensating cation and have been studied using vibrational spectroscopy including Raman and Fourier-transform infrared. Periodic trends in both the structural properties of these complexes and their vibrational spectra are presented and discussed, in particular the invariant nature of the O≡An≡O asymmetric stretching frequencies observed across the actinyl series. Electronic structure calculations were performed at a variety of levels of theory to aid in the interpretation of the vibrational data and to correlate trends in the data with the underlying electronic properties of these molecules.},
doi = {10.1021/acs.inorgchem.2c02434},
journal = {Inorganic Chemistry},
number = 39,
volume = 61,
place = {United States},
year = {Wed Sep 21 00:00:00 EDT 2022},
month = {Wed Sep 21 00:00:00 EDT 2022}
}
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