Minerals as molecules--use of aqueous oxide and hydroxide clusters to understand geochemical reactions

Large aqueous oxide ions as minerals! Minerals dissolve by repeated ligand exchange reactions and geochemists use polyoxometalate ions to establish structure-reactivity relations for environmentally important functional groups. Here, for example, are plotted the dissolution rates of two classes of minerals against rates of solvent exchanges around the corresponding aquo ions.Geochemists and environmental chemists make predictions about the fate of chemicals in the shallow earth over enormously long times. Key to these predictions is an understanding of the hydrolytic and complexation reactions at oxide mineral surfaces that are difficult to probe spectroscopically. These minerals are usually oxides with repeated structural motifs, like silicate or aluminosilicate polymers, and they expose a relatively simple set of functional groups to solution. The geochemical community is at the forefront of efforts to describe the surface reactivities of these interfacial functional groups and some insights are being acquired by using small oligomeric oxide molecules as experimental models. These small nanometer-size clusters are not minerals, but their solution structures and properties are better resolved than for minerals and calculations are relatively well constrained. The primary experimental data are simple rates of steady oxygen-isotope exchanges into the structures as a function of solution composition that can be related to theoretical results. There are only a few classes of large oxide ions for which data have been acquired and here we review examples and illustrate the general approach, which also derives directly from the use of model clusters to understand for the active core of metalloenzymes in biochemistry.