Near-infrared laboratory spectra of solid H2O/CO2 and CH3OH/CO2 ice mixtures

We present near-IR spectra of solid CO2 in H2O and CH3OH, and find they are significantly different from that of pure solid CO2. Peaks not present in either pure H2O or pure CO2 spectra become evident when the two are mixed. First, the putative theoretically forbidden CO2 (2ν3) overtone near 2.134 μm (4685 cm−1), that is absent from our spectrum of pure solid CO2, is prominent in the spectra of H2O/CO2=5 and 25 mixtures. Second, a 2.74-μm (3650 cm−1) dangling OH feature of H2O (and a potentially related peak at 1.89 μm) appear in the spectra of CO2-H2O ice mixtures, but are probably not diagnostic of the presence of CO2. Other CO2 peaks display shifts in position and increased width because of intermolecular interactions with H2O. Warming causes some peak positions and profiles in the spectrum of a H2O/CO2=5 mixture to take on the appearance of pure CO2. Absolute strengths for absorptions of CO2 in solid H2O are estimated. Similar results are observed for CO2 in solid CH3OH. Since the CO2 (2ν3) overtone near 2.134 μm (4685 cm−1) is not present in pure CO2 but prominent in mixtures, it may be a good observational (spectral) indicator of whether solid CO2 is a pure material or intimately mixed with other molecules. These observations may be applicable to Mars polar caps as well as outer Solar System bodies.