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

An absorption band at ∼4.26 μm∼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.