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Title: Establishing Cost-Effective Computational Models for the Prediction of Lanthanoid Binding in [Ln(NO3)]2+ (with Ln = La to Lu)

Journal Article · · ACS Omega
 [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)
+ Show Author Affiliations

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.

Research Organization:
Univ. of Tennessee, Knoxville, TN (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC); National Science Foundation (NSF)
Grant/Contract Number:
NA0001983; AC02-05CH11231; ACI-1548562
OSTI ID:
1491051
Alternate ID(s):
OSTI ID: 1508790
Journal Information:
ACS Omega, Vol. 4, Issue 1; ISSN 2470-1343
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

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Cited By (1)

Predicting Stability Constants for Terbium(III) Complexes with Dipicolinic Acid and 4-Substituted Dipicolinic Acid Analogues using Density Functional Theory journal November 2019

Figures / Tables (12)

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS
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