Efficient Method for an Approximate Treatment of the Coriolis Effect in Calculations of Quantum Dynamics and Spectroscopy, with Application to Scattering Resonances in Ozone
American Chemical Society
Journal of Physical Chemistry A
A numerical approach is developed to capture the effect of rotation–vibration coupling in a practically affordable way. In this approach only a limited number of adjacent rotational components are considered to be coupled, while the couplings to other rotational components are neglected. This partially coupled (PC) approach permits to reduce the size of Hamiltonian matrix significantly, which enables the calculations of ro-vibrational states above dissociation threshold (scattering resonances) for large values of total angular momentum. This method is employed here to reveal the role of the Coriolis effect in the ozone formation reaction at room temperature, dominated by large values of total angular momentum states, on the order of J = 24 and 28. We found that, overall, the effect of ro-vibrational coupling is not minor for large J. Compared to the results of symmetric top rotor approximation, where the ro-vibrational coupling is neglected, we found that the widths of scattering resonances, responsible for the lifetimes of metastable ozone states, remain nearly the same (on average), but the number of these states increases by as much as 20%. We also found that these changes are nearly the same in symmetric and asymmetric ozone isotopomers 16O18O16O and 16O16O18O. Therefore, based on the results of these calculations, the Coriolis coupling does not seem to favor the formation of asymmetric ozone molecules and thus cannot be responsible for symmetry-driven mass-independent fractionation of oxygen isotopes.
Gayday, Igor and Babikov, Dmitri, "Efficient Method for an Approximate Treatment of the Coriolis Effect in Calculations of Quantum Dynamics and Spectroscopy, with Application to Scattering Resonances in Ozone" (2021). Chemistry Faculty Research and Publications. 1039.
ADA Accessible Version
Accepted version. Journal of Physical Chemistry A, Vol. 125, No. 25 (July 1, 2021): 5661-5669. DOI. © 2021 American Chemical Society. Used with permission.