Theoretical insights into covalency driven f element separations

Lindsay E. Roy; Nicholas J. Bridges; Leigh R. Martin

doi:10.1039/c2dt31485a

Theoretical insights into covalency driven f element separations

Lindsay E. Roy, Nicholas J. Bridges, Leigh R. Martin

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54 Scopus citations

Abstract

Through Density Function Theory (DFT) calculations, we set out to understand the structures and stabilities of the aqueous phase complexes [M ^III(DTPA)-H₂O]^2- (M = Nd, Am) as well as the changes in Gibbs free energy for complexation in the gas phase and aqueous solution. All bonding analyses suggest that the preference of the DTPA ^5- ligand for Am over Nd is mainly due to electrostatic and covalent interactions from the oxygen atoms with the nitrogen chelates providing an additional, yet small, covalent interaction. These results question the exclusive use of hard and soft acids and bases (HSAB) concepts for the design of extracting reagents and suggest that hard-soft interactions may play more of a role in the separations process than previously thought.

Original language	English
Pages (from-to)	2636-2642
Number of pages	7
Journal	Dalton Transactions
Volume	42
Issue number	7
DOIs	https://doi.org/10.1039/c2dt31485a
State	Published - Feb 21 2013
Externally published	Yes

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AU - Bridges, Nicholas J.

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N2 - Through Density Function Theory (DFT) calculations, we set out to understand the structures and stabilities of the aqueous phase complexes [M III(DTPA)-H2O]2- (M = Nd, Am) as well as the changes in Gibbs free energy for complexation in the gas phase and aqueous solution. All bonding analyses suggest that the preference of the DTPA 5- ligand for Am over Nd is mainly due to electrostatic and covalent interactions from the oxygen atoms with the nitrogen chelates providing an additional, yet small, covalent interaction. These results question the exclusive use of hard and soft acids and bases (HSAB) concepts for the design of extracting reagents and suggest that hard-soft interactions may play more of a role in the separations process than previously thought.

AB - Through Density Function Theory (DFT) calculations, we set out to understand the structures and stabilities of the aqueous phase complexes [M III(DTPA)-H2O]2- (M = Nd, Am) as well as the changes in Gibbs free energy for complexation in the gas phase and aqueous solution. All bonding analyses suggest that the preference of the DTPA 5- ligand for Am over Nd is mainly due to electrostatic and covalent interactions from the oxygen atoms with the nitrogen chelates providing an additional, yet small, covalent interaction. These results question the exclusive use of hard and soft acids and bases (HSAB) concepts for the design of extracting reagents and suggest that hard-soft interactions may play more of a role in the separations process than previously thought.

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Theoretical insights into covalency driven f element separations

Abstract

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