Format of Original
Royal Society of Chemistry
Physical Chemistry Chemical Physics
Original Item ID
DOI: 10.1039/C6CP02224C; PubMed PMID: 27364351
Rigorous calculations of scattering resonances in ozone are carried out for a broad range of rotational excitations. The accurate potential energy surface of Dawes is adopted, and a new efficient method for calculations of ro–vibrational energies, wave functions and resonance lifetimes is employed (which uses hyper-spherical coordinates, the sequential diagonalization/truncation approach, grid optimization and complex absorbing potential). A detailed analysis is carried out to characterize distributions of resonance energies and lifetimes, their rotational/vibrational content and their positions with respect to the centrifugal barrier. Emphasis is on the contribution of these resonances to the recombination process that forms ozone. It is found that major contributions come from localized resonances at energies near the top of the barrier. Delocalized resonances at higher energies should also be taken into account, while very narrow resonances at low energies (trapped far behind the centrifugal barrier) should be treated as bound states. The absolute value of the recombination rate coefficient, its pressure and temperature dependencies are obtained using the energy-transfer model developed in the earlier work. Good agreement with experimental data is obtained if one follows the suggestion of Troe, who argued that the energy transfer mechanism of recombination is responsible only for 55% of the recombination rate (with the remaining 45% coming from the competing chaperon mechanism).
Teplukhin, Alexander and Babikov, Dmitri, "A Full-Dimensional Model of Ozone Forming Reaction: The Absolute Value of the Recombination Rate Coefficient, Its Pressure and Temperature Dependencies" (2016). Chemistry Faculty Research and Publications. 541.