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Title: Establishing Cost-Effective Computational Models for the Prediction of Lanthanoid Binding in [Ln(NO 3)] 2+ (with Ln = La to Lu)

Abstract

Evaluating the efficiency of predictive methods is critical to the processes of upscaling laboratory processes to full-scale operations on an industrial scale. With regard to separation of lanthanoids, there is a considerable motivation to optimize these processes because of immediate use in nuclear fuel cycle operations, nuclear forensics applications, and rare-earth metal recovery. Efficient predictive capabilities in Gibbs free energies of reaction are essential to optimize separations and ligand design for selective binding needed for various radiochemical applications such as nuclear fuel disposition and recycling of lanthanoid fission products into useful radioisotope products. Ligand design is essential for selective binding of lanthanoids, as separating contiguous lanthanoids is challenging because of the similar behavior these elements exhibit. Modeling including electronic structure calculations of lanthanoid-containing compounds is particularly challenging because of the associated computational cost encountered with the number of electrons correlated in these systems and relativistic considerations. This study evaluates the predictive capabilities of various ab initio methods in the calculation of Gibbs free energies of reaction for [Ln(NO 3)] 2+ compounds (with Ln = La to Lu), as nitrates are critical in traditional separation processes utilizing nitric acid. The composite methodologies evaluated predict Gibbs free energies of reaction for [Ln(NOmore » 3)] 2+ compounds within 5 kcal mol –1 in most cases from the target method [CCSD(T)-FSII/cc-pwCV∞Z-DK3+SO] at a fraction of the computational cost.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [4]
  1. Univ. of North Texas, Denton, TX (United States). Research Information Technology Services; Univ. of Tennessee, Knoxville, TN (United States). Inst. for Nuclear Security
  2. Univ. of Tennessee, Knoxville, TN (United States). Inst. for Nuclear Security
  3. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Nuclear Engineering
  4. Univ. of Tennessee, Knoxville, TN (United States). Inst. for Nuclear Security. Dept. of Nuclear Engineering. Radiochemistry Center of Excellence (RCOE); Y-12 National Security Complex, Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Univ. of Tennessee, Knoxville, TN (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1491051
Alternate Identifier(s):
OSTI ID: 1508790
Grant/Contract Number:  
NA0001983; AC02-05CH11231; ACI-1548562
Resource Type:
Journal Article: Published Article
Journal Name:
ACS Omega
Additional Journal Information:
Journal Volume: 4; Journal Issue: 1; Journal ID: ISSN 2470-1343
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; free energy; materials science; organic compounds and functional groups; quantum mechanical methods; rare earth salts; theory

Citation Formats

Peterson, Charles C., Penchoff, Deborah A., Auxier, John D., and Hall, Howard L. Establishing Cost-Effective Computational Models for the Prediction of Lanthanoid Binding in [Ln(NO3)]2+ (with Ln = La to Lu). United States: N. p., 2019. Web. doi:10.1021/acsomega.8b02403.
Peterson, Charles C., Penchoff, Deborah A., Auxier, John D., & Hall, Howard L. Establishing Cost-Effective Computational Models for the Prediction of Lanthanoid Binding in [Ln(NO3)]2+ (with Ln = La to Lu). United States. doi:10.1021/acsomega.8b02403.
Peterson, Charles C., Penchoff, Deborah A., Auxier, John D., and Hall, Howard L. Wed . "Establishing Cost-Effective Computational Models for the Prediction of Lanthanoid Binding in [Ln(NO3)]2+ (with Ln = La to Lu)". United States. doi:10.1021/acsomega.8b02403.
@article{osti_1491051,
title = {Establishing Cost-Effective Computational Models for the Prediction of Lanthanoid Binding in [Ln(NO3)]2+ (with Ln = La to Lu)},
author = {Peterson, Charles C. and Penchoff, Deborah A. and Auxier, John D. and Hall, Howard L.},
abstractNote = {Evaluating the efficiency of predictive methods is critical to the processes of upscaling laboratory processes to full-scale operations on an industrial scale. With regard to separation of lanthanoids, there is a considerable motivation to optimize these processes because of immediate use in nuclear fuel cycle operations, nuclear forensics applications, and rare-earth metal recovery. Efficient predictive capabilities in Gibbs free energies of reaction are essential to optimize separations and ligand design for selective binding needed for various radiochemical applications such as nuclear fuel disposition and recycling of lanthanoid fission products into useful radioisotope products. Ligand design is essential for selective binding of lanthanoids, as separating contiguous lanthanoids is challenging because of the similar behavior these elements exhibit. Modeling including electronic structure calculations of lanthanoid-containing compounds is particularly challenging because of the associated computational cost encountered with the number of electrons correlated in these systems and relativistic considerations. This study evaluates the predictive capabilities of various ab initio methods in the calculation of Gibbs free energies of reaction for [Ln(NO3)]2+ compounds (with Ln = La to Lu), as nitrates are critical in traditional separation processes utilizing nitric acid. The composite methodologies evaluated predict Gibbs free energies of reaction for [Ln(NO3)]2+ compounds within 5 kcal mol–1 in most cases from the target method [CCSD(T)-FSII/cc-pwCV∞Z-DK3+SO] at a fraction of the computational cost.},
doi = {10.1021/acsomega.8b02403},
journal = {ACS Omega},
issn = {2470-1343},
number = 1,
volume = 4,
place = {United States},
year = {2019},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acsomega.8b02403

Figures / Tables:

Table 1 Table 1: Electronic Configuration for Ln IV and Ln III43

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