The (CO2)n- clusters are thought to accommodate the excess electron by forming a localized molecular anion, or "core ion", solvated by the remaining, largely neutral CO2 molecules. Earlier studies interpreted discontinuities in the (CO2)n- photoelectron spectra to indicate that both the CO2- and C2O4- species were present in a size-dependent fashion. Here we use vibrational predissociation spectroscopy to unambiguously establish the molecular structures of the core ions in the 2 < or = n < or = 17 size range. Spectra are reported in the 2300-3800 cm(-1) region, which allows us to independently monitor the contribution of each ion through its characteristic overtone and combination bands. These signature bands are observed to be essentially intact in the larger clusters, establishing that the CO2- and C2O4- molecular ions are indeed the only electron accommodation modes at play. The size dependence of the core ion suggested in earlier analyses of the photoelectron spectra is largely confirmed, although both species are present over a range of clusters near the expected critical cluster sizes, as opposed to the prompt changes inferred earlier. Perturbations in the bands associated with the nominally neutral CO2 "solvent" molecules are correlated with the changes in the molecular structure of the core ion. These observations are discussed in the context of a diabatic model for electron delocalization over the CO2 dimer. In this picture, the driving force leading to the transient formation of the monomer ion is traced to the solvent asymmetry inherent in an incomplete coordination shell.

The Au-.CO2 ion-molecule complex has been studied by gas phase infrared photodissociation spectroscopy. Several sharp transitions can be identified as combination bands involving the asymmetric stretch vibrational mode of the CO2 ligand. Their frequencies are redshifted by several hundred cm(-1) from the frequencies of free CO2. We discuss our findings in the framework of ab initio and density-functional theory calculations, using anharmonic corrections to predict vibrational transition energies. The infrared spectrum is consistent with the formation of an aurylcarboxylate anion with a strongly bent CO2 subunit.