Strong Correlations in Actinide Redox Reactions

TL;DR

This paper models actinide redox reactions using a combination of density functional theory and a generalized Anderson impurity model to better estimate redox potentials and complex behaviors.

Contribution

It introduces a novel approach integrating DFT with an Anderson impurity model to account for strong 5f electron correlations in actinide redox chemistry.

Findings

Improved estimates of redox potentials.

Enhanced understanding of actinide complex disproportionation.

Modeling of multiple actinide redox couples.

Abstract

Reduction-oxidation (redox) reactions of the redox couples An(VI)/An(V), An(V)/An(IV), and An(IV)/An(III), where An is an element in the family of early actinides (U, Np, and Pu), as well as Am(VI)/Am(V) and Am(V)/Am(III), are modeled by combining density functional theory with a generalized Anderson impurity model that accounts for the strong correlations between the 5f electrons. Diagonalization of the Anderson impurity model yields improved estimates for the redox potentials and the propensity of the actinide complexes to disproportionate.