skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Journal Article · · ACS Omega
 [1]; ORCiD logo [2];  [3];  [4]
  1. Research Information Technology Services, University of North Texas, 225 S. Avenue B, Denton, Texas 76201, United States, Institute for Nuclear Security, University of Tennessee, 1640 Cumberland Avenue, Knoxville, Tennessee 37996, United States
  2. Institute for Nuclear Security, University of Tennessee, 1640 Cumberland Avenue, Knoxville, Tennessee 37996, United States
  3. Department of Nuclear Engineering, University of Tennessee, 301 Middle Dr., Pasqua Nuclear Engineering Bldg., Knoxville, Tennessee 37996, United States
  4. Institute for Nuclear Security, University of Tennessee, 1640 Cumberland Avenue, Knoxville, Tennessee 37996, United States, Department of Nuclear Engineering, University of Tennessee, 301 Middle Dr., Pasqua Nuclear Engineering Bldg., Knoxville, Tennessee 37996, United States, Radiochemistry Center of Excellence (RCOE), University of Tennessee, 1508 Middle Dr., Ferris Hall, Knoxville, Tennessee 37996, United States, Y-12 National Security Complex, Oak Ridge, Tennessee 37830, 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, Journal Name: ACS Omega Vol. 4 Journal 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

References (29)

The role of databases in support of computational chemistry calculations journal October 1996
Review Article: The Effects of Radiation Chemistry on Solvent Extraction: 2. A Review of Fission‐Product Extraction journal May 2009
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
The synthesis and spectroscopic characterization of an aromatic uranium amidoxime complex journal September 2014
Relativistic double-zeta, triple-zeta, and quadruple-zeta basis sets for the lanthanides La–Lu journal January 2010
Molpro: a general-purpose quantum chemistry program package: Molpro
  • Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.82
journal July 2011
Ab initio total atomization energies of small molecules — towards the basis set limit journal September 1996
Relativistic Douglas-Kroll-Hess theory: Relativistic DKH theory journal June 2011
Synthesis and Molecular Structure of a Plutonium(IV) Coordination Complex:  [Pu(NO 3 ) 2 {2,6-[(C 6 H 5 ) 2 P(O)CH 2 ] 2 C 5 H 3 NO} 2 ](NO 3 ) 2 •1.5H 2 O•0.5MeOH journal September 2000
Perspective: Fifty years of density-functional theory in chemical physics journal May 2014
Characterization of Lanthanide Complexes with Bis-1,2,3-triazole-bipyridine Ligands Involved in Actinide/Lanthanide Separation journal October 2016
Basis Set Exchange:  A Community Database for Computational Sciences journal March 2007
Cerium(IV), Neptunium(IV), and Plutonium(IV) 1,2-Phenylenediphosphonates: Correlations and Differences between Early Transuranium Elements and Their Proposed Surrogates journal November 2010
Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions journal January 1980
The correlation consistent composite approach (cc CA ): An alternative to the Gaussian-n methods journal March 2006
Comment on: “Estimating the Hartree–Fock limit from finite basis set calculations” [Jensen F (2005) Theor Chem Acc 113:267] journal December 2005
Parallel Douglas–Kroll energy and gradients in NWChem: Estimating scalar relativistic effects using Douglas–Kroll contracted basis sets journal January 2001
Synthesis, Lanthanide Coordination Chemistry, and Liquid–Liquid Extraction Performance of CMPO-Decorated Pyridine and Pyridine N -Oxide Platforms journal March 2013
Structural Analysis of the Complexation of Uranyl, Neptunyl, Plutonyl, and Americyl with Cyclic Imide Dioximes journal October 2018
Toward Chemical Accuracy in ab Initio Thermochemistry and Spectroscopy of Lanthanide Compounds: Assessing Core–Valence Correlation, Second-Order Spin–Orbit Coupling, and Higher Order Effects in Lanthanide Diatomics journal October 2017
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations journal September 2010
Structural Characteristics, Population Analysis, and Binding Energies of [An(NO 3 )] 2+ (with An = Ac to Lr) journal October 2018
Lanthanide Speciation in Potential SANEX and GANEX Actinide/Lanthanide Separations Using Tetra-N-Donor Extractants journal June 2012
Chelating properties of 2-((diphenylphosphino)methyl)pyridine N,P-dioxide and 2,6-bis((diphenylphosphino)methyl)pyridine N,P,P'-trioxide toward f-element ions journal May 1993
Separation of Americium from Lanthanides by Purified Cyanex 301 Countercurrent Extraction in Miniature Centrifugal Contactors journal January 2012
Development of Highly Selective Ligands for Separations of Actinides from Lanthanides in the Nuclear Fuel Cycle journal October 2011
Ab initio approaches for the determination of heavy element energetics: Ionization energies of trivalent lanthanides (Ln = La-Eu) journal November 2015
Correlation consistent basis sets for lanthanides: The atoms La–Lu journal August 2016
Crystallographic and Spectroscopic Characterization of Americium Complexes Containing the Bis[(phosphino)methyl]pyridine-1-oxide (NOPOPO) Ligand Platform journal February 2018

Figures / Tables (12)

Table 1(p. 3)table Table 1
Figure 1(p. 4)figure Figure 1
Table 2(p. 4)table Table 2
Figure 2(p. 5)figure Figure 2
Figure 3(p. 5)figure Figure 3
Figure 4(p. 6)figure Figure 4
Table 3(p. 6)table Table 3
Figure 5(p. 7)figure Figure 5
Table 4(p. 7)table Table 4
Figure 6(p. 8)figure Figure 6
Table 5(p. 8)table Table 5
Figure 7(p. 9)figure Figure 7

Similar Records

A new series of lanthanoid containing Keggin-type germanotungstates with acetate chelators: [{l_brace}Ln(CH{sub 3}COO)GeW{sub 11}O{sub 39}(H{sub 2}O){r_brace}{sub 2}]{sup 12-} {l_brace}Ln=Eu{sup III}, Gd{sup III}, Tb{sup III}, Dy{sup III}, Ho{sup III}, Er{sup III}, Tm{sup III}, and Yb{sup III{r_brace}}
Journal Article · Sat Jan 15 00:00:00 EST 2011 · Journal of Solid State Chemistry · OSTI ID:1491051
Synthesis, properties, and x-ray structures of the lanthanide {eta}{sup 6}-arene-bridged aryloxide dimers Ln{sub 2}(O-2,6-i-Pr{sub 2}H{sub 3}){sub 6} and their Lewis base adducts Ln(O-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}){sub 3}(THF){sub 2}(Ln = Pr, Nd, Sm, Gd, Er, Yb, Lu)
Journal Article · Wed Aug 03 00:00:00 EDT 1994 · Inorganic Chemistry · OSTI ID:1491051
Synthesis and characterization of Ln(B{sub 0.5}Mn{sub 0.5})O{sub 3} (Ln-lanthanoid; B = Ni, Co) perovskites
Journal Article · Wed Jan 01 00:00:00 EST 1997 · Materials Research Bulletin · OSTI ID:1491051
+2 more

Related Subjects

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