State-to-state quantum dynamics of the O(P3)+OH(Π2)→H(S2)+O2(Σ3g−) reaction

Abstract

The authors report a detailed quantum mechanical study of the state-to-state dynamics of the O+OH(vi=0, ji=0)→H+O2(vf,jf) reaction on an accurate HO2(X2A″) potential energy surface. The scattering dynamics was treated using a reactant coordinate based Chebyshev real wavepacket method with full Coriolis coupling. A total of 84 partial waves were calculated in order to achieve convergence up to the collision energy of 0.17 eV. The differential cross section is near forward-backward symmetric, consistent with the complex-forming mechanism. The O2 product was found to have a monotonically decaying vibrational distribution and highly excited and inverted rotational distributions, also consistent with the formation of the HO2 intermediate. These quantum mechanical results were compared with those obtained in earlier quasiclassical trajectory and statistical studies and it is shown that the statistical theory gives a reasonably good description of the product state distributions despite its inability to predict the total reaction cross section.