Fast ortho-to-para conversion of molecular hydrogen in chemisorption and matrix-isolation systems.

Molecular hydrogen has two nuclear-spin modifications called ortho and para. Because of the symmetry restriction with respect to permutation of the two protons, the ortho and para isomers take only odd and even values of the rotational quantum number, respectively. The ortho-to-para conversion is promoted in condensed systems, to which the excess rotational energy and spin angular momentum are transferred. We review recent studies on fast ortho-to-para conversion of hydrogen in molecular chemisorption and matrix isolation systems, discussing the conversion mechanism as well as rotational-relaxation pathways.

Nuclear-spin conversion analysis of ν2 + ν4 combination band of crystalline methane in phase II.

We conducted reflection-absorption infrared spectroscopy in an ultrahigh vacuum and observed the ν2 + ν4 combination band of crystalline methane in phase II, where the rotating and librating species coexist. We analyzed the time- and temperature-dependence of the spectrum due to the nuclear-spin conversion of methane to update the assignment of the rotational and librational structure of this band. The conversion analysis performed in the present work will also be applicable to the detailed assignments of overtones and other combination bands.

Terahertz and mid-infrared spectroscopy of matrix-isolated clusters and matrix-sublimation ice of D2O.

We have established an apparatus for terahertz and mid-infrared spectroscopy in an ultrahigh vacuum and have measured absorption spectra of D2O clusters trapped in solid Ar. To assign terahertz absorption peaks due to the D2O dimer, trimer, and tetramer, the dependence of the spectrum on the annealing temperature and D2O dilution was analyzed. The assignment was also examined by ab initio calculations with the use of the "our own N-layered integrated molecular orbital and molecular mechanics" method, where the flexibility of surrounding Ar atoms was systematically incorporated. We identified all the intermolecular fundamentals of the dimer and those with significant intensities of the trimer and tetramer, whose structural symmetries were revealed to be broken down. After isolating the D2O clusters in solid Ar, we sublimated only Ar atoms to leave behind matrix-sublimation ice, which was found to be amorphous- or crystal-like depending on the formation conditions: the dilution and sublimation temperature. The crystallinity of matrix-sublimation ice was determined by decomposing its terahertz spectrum into the spectra of amorphous and crystalline ices. Since the crystallinity got higher by raising the dilution and sublimation temperature, the diffusion of the D2O monomer on the surface of sublimating solid Ar was found to be crucial to the crystallization of the sublimation ice.

Spectroscopic determination of interconversion rates among three nuclear spin isomers of methane in crystalline II.

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.

Asymmetric and symmetric absorption peaks observed in infrared spectra of CO2 adsorbed on TiO2 nanotubes.

Infrared spectra of CO2 physisorbed on titania nanotubes (TiNTs), predominantly in the anatase polymorph, were measured at 81 K. Asymmetric and symmetric absorption peaks due to the antisymmetric stretch vibration (ν3) of CO2 were observed at 2340 cm(-1) and 2350 cm(-1), respectively. On the basis of the exposure- and time-dependence of the spectrum, the 2340 cm(-1) peak was attributed to CO2 at the defective sites related to subsurface O vacancies (Vos) while the 2350 cm(-1) peak was assigned to that at the fivefold coordinated Ti(4+) sites. It was found that the generalized Fano line shape was well fitted to the 2340 cm(-1) peak. We also observed an absorption peak at 2372 cm(-1), which was attributed to the combination band of ν3 and the external mode of CO2 at Ti(4+).

Infrared spectroscopic investigation of nuclear spin conversion in solid CH4.

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.