Quantum-mechanical calculations on pressure and temperature dependence of three-body recombination reactions: application to ozone formation rates.

Journal article

A quantum-mechanical model is designed for the calculation of termolecular association reaction rate coefficients in the low-pressure fall-off regime. The dynamics is set up within the energy transfer mechanism and the kinetic scheme is the steady-state approximation. We applied this model to the formation of ozone O + O2 + M --> O3 + M for M = Ar, making use of semiquantitative potential energy surfaces. The stabilization process is treated by means of the vibrational close-coupling infinite order sudden scattering theory. Major approximations include the neglect of the O3 vibrational bending mode and rovibrational couplings. We calculated individual isotope-specific rate constants and rate constant ratios over the temperature range 10-1000 K and the pressure fall-off region 10(-7)-10(2) bar. The present results show a qualitative and semiquantitative agreement with available experiments, particularly in the temperature region of atmospheric interest.

Authors: Charlo, D; Clary, D

• Publication status: Published
• Journal: Journal of chemical physics
• Volume: 120
• Issue: 6
• Pages: 2700-2707
• Publication date: 2004-02-01
• DOI: 10.1063/1.1635361
• EISSN: 1089-7690
• ISSN: 0021-9606
• Language: English