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Title: 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:
 [1]; ORCiD logo [1];  [2];  [2]; ORCiD logo [2]
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  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. 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.
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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
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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.
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@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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