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Title: Quantum chemistry benchmarking of binding and selectivity for lanthanide extractants

Abstract

Computer-aided screening methods facilitate the discovery of new extractants for heavy and rare-earth metal separations. In this work, we have benchmarked the accuracy of different quantum chemistry methods for calculating extractant binding energies and selectivities. Specifically, we compare calculated data from different exchange correlation functionals (B3LYP-D3, ωB97X-D3, and M06-L) and different basis sets (including large-core effective core potentials and all-electron basis sets). We report aqueous-phase binding energy and selectivity trends for 1:1 and 3:1 extractant/lanthanide models for the complexes. We find that binding selectivities are not particularly sensitive to model chemistry, but binding energies are sensitive. Furthermore, calculated trends in selectivity using 3:1 extractant/lanthanide models are in better agreement with available experimental trends than trends using 1:1 extractant/lanthanide models. Lastly, we find that the B3LYP-D3/6-31 + G* model chemistry with the Stuttgart large-core relativistic effective core potentials on the lanthanide sufficiently reproduces results from larger basis set calculations and is confirmed as suitable for relatively fast and efficient screening of lanthanide binding energies and selectivities.

Authors:
 [1];  [2];  [1]; ORCiD logo [1]
  1. Univ. of Pittsburgh, PA (United States). Dept. of Chemical & Petroleum Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1458377
Alternate Identifier(s):
OSTI ID: 1399596
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
International Journal of Quantum Chemistry
Additional Journal Information:
Journal Volume: 118; Journal Issue: 7; Journal ID: ISSN 0020-7608
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
97 MATHEMATICS AND COMPUTING; 36 MATERIALS SCIENCE; binding energies; chelants; extractants; lanthanides; selectivities

Citation Formats

Vo, Minh Nguyen, Bryantsev, Vyacheslav S., Johnson, J. Karl, and Keith, John A. Quantum chemistry benchmarking of binding and selectivity for lanthanide extractants. United States: N. p., 2017. Web. doi:10.1002/qua.25516.
Vo, Minh Nguyen, Bryantsev, Vyacheslav S., Johnson, J. Karl, & Keith, John A. Quantum chemistry benchmarking of binding and selectivity for lanthanide extractants. United States. doi:10.1002/qua.25516.
Vo, Minh Nguyen, Bryantsev, Vyacheslav S., Johnson, J. Karl, and Keith, John A. Sat . "Quantum chemistry benchmarking of binding and selectivity for lanthanide extractants". United States. doi:10.1002/qua.25516. https://www.osti.gov/servlets/purl/1458377.
@article{osti_1458377,
title = {Quantum chemistry benchmarking of binding and selectivity for lanthanide extractants},
author = {Vo, Minh Nguyen and Bryantsev, Vyacheslav S. and Johnson, J. Karl and Keith, John A.},
abstractNote = {Computer-aided screening methods facilitate the discovery of new extractants for heavy and rare-earth metal separations. In this work, we have benchmarked the accuracy of different quantum chemistry methods for calculating extractant binding energies and selectivities. Specifically, we compare calculated data from different exchange correlation functionals (B3LYP-D3, ωB97X-D3, and M06-L) and different basis sets (including large-core effective core potentials and all-electron basis sets). We report aqueous-phase binding energy and selectivity trends for 1:1 and 3:1 extractant/lanthanide models for the complexes. We find that binding selectivities are not particularly sensitive to model chemistry, but binding energies are sensitive. Furthermore, calculated trends in selectivity using 3:1 extractant/lanthanide models are in better agreement with available experimental trends than trends using 1:1 extractant/lanthanide models. Lastly, we find that the B3LYP-D3/6-31 + G* model chemistry with the Stuttgart large-core relativistic effective core potentials on the lanthanide sufficiently reproduces results from larger basis set calculations and is confirmed as suitable for relatively fast and efficient screening of lanthanide binding energies and selectivities.},
doi = {10.1002/qua.25516},
journal = {International Journal of Quantum Chemistry},
number = 7,
volume = 118,
place = {United States},
year = {2017},
month = {10}
}

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