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The thermally activated recombination reaction O+O2→O3 is observed in solid xenon matrices and in free-standing crystals of xenon at 14–25 K on the time scale 102–105 s. The reactants are prepared as spatially separated O...O2 pairs immobilized in solid Xe at 10 K by 266 nm photodissociation of O3 precursor molecules. The temperature dependence of the ozone recovery rate yields an activation energy for diffusion of O atoms in solid xenon of 2.0±0.5 kJ/mol. This value also represents an upper limit to the potential energy barrier to the O+O2 recombination reaction itself. In dilute samples (mole fraction of ozone less than 2×10-4) more than 90% of the initial O3 is recovered during the warming cycle. Only a small fraction of O atoms (<20%) escape geminate recombination with the partner oxygen molecule within the pair and react with other O2 molecules or O atoms. The experimental results are interpreted within the framework of a continuous diffusion model in which the initial spatial distribution of reactants is nonrandom. © 1996 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Wepresent a general response function formalism describing thecontribution of orientational dynamics of molecules at interfacesto spectroscopic line shapes in vibrational sum frequency generation(SFG). When reorientation occurs on the time scale comparable to vibrationaldephasing, its dynamics can be extracted from polarization-selectedSFG spectral line shapes. Unique features of orientational motionat interfaces are (1) the anisotropic case-specific equilibrium orientationaldistribution and (2) possible dynamic anisotropy (e.g., differentin-plane versus out-of-plane relaxation rates), both of which mustbe taken into account. Within the small-step rotational diffusionmodel, we present solutions for two cases, the weak-confinement model,applicable when the deviations from the isotropic case are not severe,and the wobbling-in-a-cone model, which considers a hard-wall orientingpotential. SFG line shapes are calculated for a rod-like chromophoreas a function of the rotational diffusion rate. For certain equilibriumorientational distributions, orientational dynamics may result inanomalous bi-Lorentzian line shapes (two Lorentzians of differentwidths centered and the same frequency). [ABSTRACT FROM AUTHOR]