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Title: Structural Analysis of the Complexation of Uranyl, Neptunyl, Plutonyl, and Americyl with Cyclic Imide Dioximes

Abstract

Knowledge-based design of extracting agents for selective binding of actinides is essential in stock-pile stewardship, environmental remediation, separations, and nuclear fuel disposal. Robust computational protocols are critical for in depth understanding of structural properties and to further advance the design of selective ligands. In particular, rapid radiochemical separations require predictive capabilities for binding in the gas phase. This study focuses on gas-phase binding preferences of cyclic imide dioximes to uranyl, neptunyl, plutonyl, and americyl. Structural properties, electron withdrawing effects, and their effects on binding preferences are studied with natural bond-order population analysis. The aromatic amidoximes are found to have a larger electron-donation effect than the aliphatic amidoximes. As a result, it is also found that plutonyl is more electron withdrawing than uranyl, neptunyl, and americyl when bound to the cyclic imide dioximes studied.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [4];  [5];  [5]; ORCiD logo [5];  [6];  [7]
  1. Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Univ. of North Texas, Denton, TX (United States)
  3. Univ. of Notre Dame, Notre Dame, IN (United States)
  4. Y-12 National Security Complex, Oak Ridge, TN (United States)
  5. Univ. of Tennessee, Knoxville, TN (United States)
  6. Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
  7. Univ. of Tennessee, Knoxville, TN (United States); Y-12 National Security Complex, Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory, Oak Ridge Leadership Computing Facility (OLCF); Univ. of Tennessee, Knoxville, TN (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC); USDOE National Nuclear Security Administration (NNSA), Office of Defense Nuclear Security (NA-70)
OSTI Identifier:
1478699
Alternate Identifier(s):
OSTI ID: 1480269; OSTI ID: 1485204
Report Number(s):
BNL-209498-2018-JAAM
Journal ID: ISSN 2470-1343; SC0012704
Grant/Contract Number:  
NA0001983; SC0012704
Resource Type:
Journal Article: Published Article
Journal Name:
ACS Omega
Additional Journal Information:
Journal Volume: 3; Journal Issue: 10; Journal ID: ISSN 2470-1343
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; Coordination chemistry (Organomet.); Electronic structure; Entropy; Free energy; Materials science; Molecular structure; Organic compounds and Functional groups; Vibrational frequency

Citation Formats

Penchoff, Deborah A., Peterson, Charles C., Camden, Jon P., Bradshaw, James A., Auxier, II, John D., Schweitzer, George K., Jenkins, David M., Harrison, Robert J., and Hall, Howard L. Structural Analysis of the Complexation of Uranyl, Neptunyl, Plutonyl, and Americyl with Cyclic Imide Dioximes. United States: N. p., 2018. Web. doi:10.1021/acsomega.8b02068.
Penchoff, Deborah A., Peterson, Charles C., Camden, Jon P., Bradshaw, James A., Auxier, II, John D., Schweitzer, George K., Jenkins, David M., Harrison, Robert J., & Hall, Howard L. Structural Analysis of the Complexation of Uranyl, Neptunyl, Plutonyl, and Americyl with Cyclic Imide Dioximes. United States. doi:10.1021/acsomega.8b02068.
Penchoff, Deborah A., Peterson, Charles C., Camden, Jon P., Bradshaw, James A., Auxier, II, John D., Schweitzer, George K., Jenkins, David M., Harrison, Robert J., and Hall, Howard L. Wed . "Structural Analysis of the Complexation of Uranyl, Neptunyl, Plutonyl, and Americyl with Cyclic Imide Dioximes". United States. doi:10.1021/acsomega.8b02068.
@article{osti_1478699,
title = {Structural Analysis of the Complexation of Uranyl, Neptunyl, Plutonyl, and Americyl with Cyclic Imide Dioximes},
author = {Penchoff, Deborah A. and Peterson, Charles C. and Camden, Jon P. and Bradshaw, James A. and Auxier, II, John D. and Schweitzer, George K. and Jenkins, David M. and Harrison, Robert J. and Hall, Howard L.},
abstractNote = {Knowledge-based design of extracting agents for selective binding of actinides is essential in stock-pile stewardship, environmental remediation, separations, and nuclear fuel disposal. Robust computational protocols are critical for in depth understanding of structural properties and to further advance the design of selective ligands. In particular, rapid radiochemical separations require predictive capabilities for binding in the gas phase. This study focuses on gas-phase binding preferences of cyclic imide dioximes to uranyl, neptunyl, plutonyl, and americyl. Structural properties, electron withdrawing effects, and their effects on binding preferences are studied with natural bond-order population analysis. The aromatic amidoximes are found to have a larger electron-donation effect than the aliphatic amidoximes. As a result, it is also found that plutonyl is more electron withdrawing than uranyl, neptunyl, and americyl when bound to the cyclic imide dioximes studied.},
doi = {10.1021/acsomega.8b02068},
journal = {ACS Omega},
issn = {2470-1343},
number = 10,
volume = 3,
place = {United States},
year = {2018},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acsomega.8b02068

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: (a) AnO2(HA)(NO3)(CH3OH), (b) AnO2(HB)(NO3)(CH3OH), (c) AnO2(HC)(NO3)(CH3OH), (d) AnO2(HA)2, (e) AnO2(HB)2, (f) AnO2(HC)2. [Green = U, Np, Pu, and Am; red = oxygen; blue = nitrogen; grey = carbon; white = hydrogen.]

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