Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory

Vukovic, Sinisa; Hay, Benjamin P.; Bryantsev, Vyacheslav S.

doi:10.1021/acs.inorgchem.5b00264

Title: Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory

Journal Article · Thu Apr 02 00:00:00 EDT 2015 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.5b00264· OSTI ID:1224161

Vukovic, Sinisa ^[1]; Hay, Benjamin P. ^[1]; Bryantsev, Vyacheslav S. ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

The ability to predict the equilibrium constants for the formation of 1:1 uranyl:ligand complexes (log K₁values) provides the essential foundation for the rational design of ligands with enhanced uranyl affinity and selectivity. We also use density functional theory (B3LYP) and the IEFPCM continuum solvation model to compute aqueous stability constants for UO₂²⁺ complexes with 18 donor ligands. Theoretical calculations permit reasonably good estimates of relative binding strengths, while the absolute log K₁ values are significantly overestimated. Accurate predictions of the absolute log K₁ values (root mean square deviation from experiment < 1.0 for log K₁ values ranging from 0 to 16.8) can be obtained by fitting the experimental data for two groups of mono and divalent negative oxygen donor ligands. The utility of correlations is demonstrated for amidoxime and imide dioxime ligands, providing a useful means of screening for new ligands with strong chelate capability to uranyl.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1224161

Journal Information:: Inorganic Chemistry, Vol. 54, Issue 8; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 77 works

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