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Infrared spectra of O2- x (CO2)n clusters (n=1-6): asymmetric docking at the pi* orbital.

Isolated superoxide ions solvated by CO2 have been studied by infrared photodissociation spectroscopy and density-functional theory, using CO2 evaporation upon infrared excitation of the O2- x (CO2)n (n=1-6) parent ions. We can assign the observed frequencies to the asymmetric stretch vibration and its combination bands with the symmetric stretch and the overtone of the bending vibration of CO2 in various binding situations. We interpret our findings with the help of density-functional theory. Our data suggest that only one CO2 moiety binds strongly to the O2-, whereas the rest of the CO2 molecules are weakly bound, which is consistent with the experimental spectra. The lobes of the pi* orbital of O2- provide a template for the structure of the microsolvation environment.