Synthesis of experimental models for molecular inorganic geochemistry—A review with examples

We are observing an sharp evolution within low-temperature geochemistry away from thermodynamics and deep geologic time toward molecular processes, particularly those at mineral or bacterial surfaces, and disequilibria. This evolution has led to a new cooperation between Earth scientists and inorganic chemists who synthesize aqueous metal-(hydr)oxide clusters as models for enzyme centers and hydrolytic products. If geochemists too can embrace these methods, we can create experimental models to answer some of the key questions posed about minerals and their reactions with aqueous solutions. In this paper we lay out the areas where there is overlap in these two fields using particular examples and emphasize how skills from each subdiscipline can benefit the whole.The central point is that this the fusion is extraordinarily healthy to both fields, as inorganic chemistry expands to embrace natural processes and as geochemists embrace methods of molecular synthesis and new useful, yet unnatural materials, that have traditionally been considered exotic. The motivation for this cooperation is the emphasis on reaction mechanisms between surface functional groups on minerals, or cells, in water. By mechanisms is meant the key atoms and molecular motions that cause the reaction to occur. For aqueous reactions, the key variables are: the number and character of inner-sphere ligands and metals; the Brønsted acidity of key atoms in cleavable bonds and the accessibility of the key atoms to solutes. These variables can be studied systematically in experimental clusters and coupled directly to advances in simulation.