Recombination of ozone via the chaperon mechanism.
The recombination of ozone via the chaperon mechanism, i.e., ArO+O2 --> Ar+O3 and ArO2+O --> Ar+O3, is studied by means of classical trajectories and a pairwise additive Ar-O3 potential energy surface. The recombination rate coefficient has a strong temperature dependence, which approximately can be described by T(-n) with n approximately 3. It is negligible for temperatures above 700 K or so, but it becomes important for low temperatures. The calculations unambiguously affirm the conclusions of Hippler et al. [J. Chem. Phys. 93, 6560 (1990)] and Luther et al. [Phys. Chem. Chem. Phys. 7, 2764 (2005)] that the chaperon mechanism makes a sizable contribution to the recombination of O3 at room temperature and below. The dependence of the chaperon recombination rate coefficient on the isotopomer, studied for two different isotope combinations, is only in rough qualitative agreement with the experimental data. The oxygen atom isotope exchange reaction involving ArO and ArO2 van der Waals complexes is also investigated; the weak binding of O or O2 to Ar has only a small effect.
Max-Planck-Institut für Dynamik und Selbstorganisation, D-37073 Göttingen, Germany. mivanov@gwdg.de
Mikhail V
MV
Ivanov
Reinhard
R
Schinke