Infrared Spectroscopic Study of Methane Ice, Pure and in Mixtures with Polar (H2O) and Nonpolar (N2) Molecules.

Mid-infrared studies of fundamental modes of ices of pure CH4 and its mixtures with polar (H2O) and nonpolar (e.g., N2) molecules are essential in order to learn the state of aggregation and thermal history of ices present in the interstellar medium and outer solar system bodies. Such data will be useful in the interpretation of observational data from the James Webb Space Telescope. Using an ultrahigh vacuum apparatus, we conducted reflection-absorption infrared spectroscopy measurements in the mid-IR range of pure methane ice and methane-containing ice mixtures of interest to interstellar and solar system ice chemistry, e.g., with H2O and N2 molecules. We found that nuclear spin conversion (NSC) in solid methane and its crystalline structures is affected─in different ways─by the presence of H2O and N2. Specifically, we found a relationship between the thickness and the solid-state ordering transformation in methane thin films. This new study of the NSC of pure CH4 ice and of the CH4:H2O ice mixture at 7 K is carried out in relation to the segregation of H2O using the ν1 and ν2 IR inactive modes of methane. The diffusion of N2 and CH4 in the CH4:N2 ice mixture with temperature cycling has been studied to obtain the relationship between IR features and the state of aggregation of the ice.

Infrared Spectroscopic Study of Solid Methane: Nuclear Spin Conversion of Stable and Metastable Phases.

Infrared spectroscopy was employed to study thin films of solid methane at low temperatures. We report new measurements of temporal changes of infrared spectra of methane ice in the ν3 and ν4 bands due to nuclear spin conversion upon rapid cooling from 30 to 6.0-11.0 K. The relaxation rates of the nuclear spin were found to be a function of temperature. The activation energy associated with the relaxation has been determined over an extended temperature range. We also found a new metastable phase of methane ice upon deposition at T < 7 K. After the deposition at 6 K and annealed to a higher temperature, a phase transition from the metastable phase to a stable crystalline phase takes place. We found that the relaxation has different activation energies below and above 8.5 K. From a quantitative analysis of the ν3 and ν4 IR bands, we suggest that the metastable phase is a crystalline phase with a degree of orientational disorder between the two known stable solid phases.