Carbon dioxide on planetary bodies: Theoretical and experimental studies of molecular complexes

An absorption band at ∼4.26 μm wavelength attributed to the asymmetric stretching mode of CO in CO₂ has been found on two satellites of Jupiter and several satellites of Saturn. The wavelength of pure CO₂ ice determined in the laboratory is 4.2675 μm, indicating that the CO₂ on the satellites occurs either trapped in a host material, or in a chemical or physical complex with other materials, resulting in a blue shift of the wavelength of the band. In frequency units, the shifts in the satellite spectra range from 3.7 to 11.3 cm⁻¹. We have performed ab initio quantum chemical calculations of CO₂ molecules chemically complexed with one, two, and more H₂O molecules and molecules of CH₃OH to explore the possibility that the blue shift of the band is caused by chemical complexing of CO₂ with other volatile materials. Our computations of the harmonic and anharmonic vibrational frequencies using high levels of theory show a frequency shift to the blue by 5 cm⁻¹ from pure CO₂ to CO-H₂O, and an additional 5 cm⁻¹ from CO₂-H₂O to CO₂-2H₂O. Complexing with more than two H₂O molecules does not increase the blue shift. Complexes of CO₂ with one molecule of CH₃OH and with one CH₃OH plus one H₂O molecule produce smaller shifts than the CO₂-2H₂O complex. Laboratory studies of CO₂:H₂O in a solid N₂ matrix also show a blue shift of the asymmetric stretching mode.