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Rotational relaxation measurements in ozone - Temperature and collision partner effects

Time-resolved infrared double resonance experiments have been conducted on ozone mixtures in order to determine rotational relaxation rates. A pulsed CO2 laser pumps a nu(3)-ground state transition, while a diode laser is tuned to a hot band transition so that the relaxation process in nu(3) = 1 may be observed. Nitrogen, oxygen, rare gas, and self-relaxation rates have been measured, and the temperature dependence of these rates has been investigated over the 200-300 K range.

Flannery, C. C.↗

Isotope Effects in Collisional VT Relaxation of Molecular Hydrogen

A simple exponential-potential model of molecular collisions leads to a two-parameter analytic expression for rates of collisionally induced vibrational-translation (VT) energy exchange that has been shown to be accurate over variations of orders of magnitude as a function of temperature in a variety of systems. This includes excellent agreement with reported experimental and theoretical results for the fundamental self-relaxation rate of molecular hydrogen H2(v = 1) + H2 yields H2(v = 0) + H2. The analytic rate successfully follows the five-orders-of-magnitude change in experimental values for the temperature range 50-2000 K. This approach is now applied to isotope effects in the vibrational relaxation rates of excited HD and D2 in collision with H2: HD(v = 1)+H2 yields HD(v = 0)+H2 and D2(v = 1)+H2 yields D2(v = 0)+H2. The simplicity of the analytic expression for the thermal rate lends itself to convenient application in modeling the evolving vibrational populations of molecular hydrogen in shocked astrophysical environments.

Bieniek, R. J.↗