Interaction of CO 2 with Atomic Manganese in the Presence of an Excess Negative Charge Probed by Infrared Spectroscopy of [Mn(CO 2 ) n ] - Clusters.

We report infrared photodissociation spectra of manganese-CO2 cluster anions, [Mn(CO2 )n ]- (n = 2-10) to probe structural motifs characterizing the interaction between Mn and CO2 in the presence of an excess electron. We interpret the experimental spectra through comparison with infrared spectra predicted from density functional theory calculations. The cluster anions consist of core ions combining a Mn atom with a variety of ligands, solvated by additional CO2 molecules. Structural motifs of ligands evolve with increasing cluster size from simple monodentate and bidentate CO2 ligands to oxalate ligands and combinations of these structural themes.