Toward the Modeling of the Oxidation of Small Metal and Metalloid Molecules

Abstract

Oven based entrainment flow and supersonic expansion techniques are used to form small metal and metalloid molecules and to study their unusual oxidation behavior. These metal and metalloid molecules oxidize to form not only a distinct class of metal atom grouped cluster oxides and halides under kinetically as opposed to thermodynamically controlled conditions but also unusual (unexpected) excited electronic state product distributions. We exemplify this behavior by considering the optical signatures associated with the formation of the asymmetric silver and copper clustered oxides from the silver and copper cluster oxidation reactions. We also contrast the emission spectra generated for the asymmetric and symmetric isomers of Cu2O, comparing these with theory. A subset of the oxidation studies touches on the sodium trimer - halogen atom reactions, (Na3 - X(Cl,Br,I)), which create a continuous electronic population inversion based on the chemical pumping of Na2 with laser amplification throughout the visible and into the ultraviolet. The study of highly exothermic oxidation processes also yields interesting surprises concerning even the diatomic metal halides. This is exemplified by comparing the Bix + F2 and Bix + F chemiluminescent reactions, extracting parameters for several new low-lying excited electronic states and obtaining an estimate of the BiF bond dissociation energy notably higher than that previously recommended in the literature.