Computational investigation of the speciation of uranyl gluconate complexes in aqueous solution.

The geometries, relative energies and spectroscopic properties of a range of D-gluconate complexes of uranyl(VI) are studied computationally using density functional theory. The effect of pH is accommodated by varying the number of water and hydroxide ligands accompanying gluconate in the equatorial plane of the uranyl unit. For 1 : 1 complexes, the calculated uranyl ν(asym) stretching frequency decreases as pH increases, in agreement with previous experimental data. Three different gluconate chelating modes are studied. Their relative energies are found to be pH dependent, although the energetic differences between them are not sufficient to exclude the possibility of multiple speciation. (13)C NMR chemical shifts are calculated for the coordinated gluconate in the high pH mimics, and show good agreement with experimental data, supporting the experimental conclusion that the six-membered chelate ring is favoured at high pH. Attempts to improve the description of the aqueous environment via the addition of second solvation shell water molecules resulted in significantly worse agreement with experiment for ν(asym). The effect of increasing the gluconate concentration is modelled by calculating 1 : 2 and 1 : 3 uranyl : D-gluconate complexes.