Infrared spectra of solid CH4 were studied in the ν3 and ν4 vibrational regions. The phase I crystal around 30 K showed broad absorption bands, whereas the phase II crystal at 6.9-10.3 K exhibited splitting of these bands after annealing above 20 K. The split peaks were assigned to the librating and almost freely rotating molecules in phase II on the basis of the peak spacings and time evolution of the peak intensities. From the quantitative analysis of the temporal changes of the R(0) and R(1) peak intensities, the relaxation rates of the numbers of molecules with J = 0 (I = 2) and J = 1 (I = 1) were determined in the temperature range of 6.9-10.3 K. We fitted the function resulting from a combination of direct and indirect relaxation processes mediated by phonons to the temperature dependence of these rates and obtained the activation energies of the indirect process: C ≃ 36 K. Since this value is higher than the energies of perturbed J = 2 states relative to the J = 1 state, we argue that the nuclear spin conversion through the J = 3 state also takes place.

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The infrared absorption spectra of D2O monomers and clusters isolated in rare-gas matrices were systematically reinvestigated under the control of the following factors: the D2O concentration, deposition rate, heating temperature, and rare-gas species. We clearly show that the cluster-size distribution is dependent on not only the D2O concentration but also the deposition rate of a sample; as the rate got higher, smaller clusters were preferentially formed. Under the heating procedures at different temperatures, the cluster-size growth was successfully observed. Since the monomer diffusion was not enough to balance the changes in the column densities of the clusters, the dimer diffusion was likely to contribute the cluster growth. The frequencies of the bonded-OD stretches of (D2O)k with k = 2-6 were almost linearly correlated with the square root of the critical temperature of the matrix material. Additional absorption peaks of (D2O)2 and (D2O)3 in a Xe matrix were assigned to the species trapped in tight accommodation sites.

We measured infrared absorption spectra of crystalline II of CH4 and succeeded in detecting a prominent Q(2) peak in the ν3 vibrational region by rapid cooling after annealing as well as previously reported rovibrational and librational-vibrational peaks. The integral intensities of the R(0), R(1), and Q(2) peaks were found to show biexponential dependence on time. This clearly demonstrates the interconversion among the three nuclear-spin isomers occupying low-lying rotational levels. The two relaxation rates obtained by biexponential fitting were (0.48, 2.3), (1.1, 4.1), (2.3, 5.1), and (3.4, 15.3) in units of inverse hour (h−1) at 5.2, 6.0, 6.5, and 7.0 K, respectively.

Using infrared-active solvents of CH4 and CD4 for matrix isolation, we measured infrared spectra of H2O and D2O clusters at 7 K. The solute-concentration dependence of the spectrum of H2O clusters in a CH4 matrix was investigated and was used for the peak assignment. Annealing procedures were found to promote the size growth of water clusters in methane matrices for all the combinations of (H2O, CH4), (H2O, CD4), (D2O, CH4), and (D2O, CD4). We also monitored the ν3 absorption due to methane to find the annealing-induced structural change only of solid CH4. The matrix effects on the vibrations of the clusters are discussed on the basis of “Tc plots”, where their frequencies are plotted as a function of the square root of the matrix critical temperature, Tc. The obtained plots assure the validity of the assignment of the cluster peaks.

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