State-to-state reaction probabilities for the H+O2(v,j)-->O+OH(v',j') reaction on three potential energy surfaces.
We report state-to-state and total reaction probabilities for J=0 and total reaction probabilities for J=2 and 4 for the title reaction, both for ground-state and initially rovibrationally excited reactants. The results for three different potential energy surfaces are compared and contrasted. The potential energy surfaces employed are the DMBE IV surface by Pastrana et al. [J. Phys. Chem. 94, 8073 (1990)], the surface by Troe and Ushakov (TU) [J. Chem. Phys. 115, 3621 (2001)], and the new XXZLG ab initio surface by Xu et al. [J. Chem. Phys. 122, 244305 (2005)]. Our results show that the total reaction probabilities from both the TU and XXZLG surfaces are much smaller in magnitude for collision energies above 1.2 eV compared to the DMBE IV surface. The three surfaces also show different behavior with regards to the effect of initial state excitation. The reactivity is increased on the XXZLG and the TU surfaces and decreased on the DMBE IV surface. Vibrational and rotational product state distributions for the XXZLG and the DMBE IV surface show different behaviors for both types of distributions. Our results show that for energies above 1.25 eV the dynamics on the DMBE IV surface are not statistical. However, there is also evidence that the dynamics on the XXZLG surface are not purely statistical for energies above the onset of the first excited product vibrational state v'=1. The magnitude of the total reaction probability is decreased for J>0 for the DMBE IV and the XXZLG surfaces for ground-state reactants. However, for initially rovibrationally excited reactants, the total reaction probability does not decrease as expected for both surfaces. As a result the total cross section averaged over all Boltzmann accessible rotational states may well be larger than the cross section reported in the literature for j=1.
Hankel
Marlies
M
Centre for Computational Molecular Science, Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, QLD 4072, Australia. m.hankel@uq.edu.au
Smith
Sean C
SC
Meijer
Anthony J H M
AJ
D002627:Chemistry, Physical / Q000379:methods*; D006859:Hydrogen / Q000737:chemistry*; D008432:Mathematical Computing; D008956:Models, Chemical; D015233:Models, Statistical; D008962:Models, Theoretical; D010100:Oxygen / Q000737:chemistry*; D011336:Probability; D011789:Quantum Theory; D013499:Surface Properties; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
D014867:Water; D006859:Hydrogen; D010100:Oxygen