The highly tunable formation of (oxyhydr)oxides from polyatomic ion precursors, referred to here as clusters, is at the heart of mineralogy and aqueous geochemical reactions. The distribution of a variety of distinct oxygen functional groups that clusters expose to the solvent makes them useful geochemical models. Thus clusters provide a platform for studies of partitioning reactions that are of fundamental importance to mineral-water reactivity. To fully capitalize on clusters as geochemical models, as well as to answer fundamental questions about solid formation and tunability, we must better understand the chemical building blocks of pre-nucleation clusters, how ligands and counterions influence the products formed, and cluster reactivity.  Using a computational retrosynthesis approach, we isolate and probe numerous mono, di, and trimeric Al and Fe units, using electronic structure theory to detail how complexing ligands and counterions tune molecular orbitals and geometry.  The calculations are used to form a basis of suggested key prenucleation reaction pathways and intermediates.

Theoretical studies of prenucleation clusters

253rd National Meeting (2017)

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