A quasiclassical trajectory study of the reaction H + O2 <==> OH + O with the O2 reagent vibrationally excited.
Quasiclassical trajectories have been computed on the Melius-Blint (MB) Potential Energy Surface (PES) and on the Double Many-Body Expansion (DMBE) IV PES of Pastrana et al. describing the H + O(2) <==> OH + O reaction with the nonrotating (J = 0) O(2) reagent vibrationally excited to levels v = 6, 7, 8, 9, and 10 at four temperatures: 1000, 2000, 3000, and 4000 K. The vibrational energy levels were selected by using a semiclassical Einstein-Brillouin-Keller (EBK) quantization procedure while the relative translational energy was sampled from a Boltzmann weighted distribution. The rate coefficient for the formation of the OH + O products is seen to increase monotonically with quantum number and nearly monotonically with temperature. On the MB PES, at T = 1000 K, the total rate coefficient increases by a factor of 5.2 as the initial vibrational quantum number of the O(2) diatom increases from v = 6 to v = 10. For T = 2000 K, this factor drops to 3.3, to 2.9 for T = 3000 K, and to 2.5 for T = 4000 K. On the DMBE IV PES, at T = 1000 K the total rate coefficient increases by a factor of 4.1 as the initial vibrational quantum number of the O(2) diatom increases from v = 6 to v = 10. For T = 2000 K, this factor drops to 3.5, to 2.1 for T = 3000 K, and to 2.0 for T = 4000 K. The less-direct group (defined below) of trajectories is sensitive to the initial O(2) vibrational excitation in several different temperature ranges, apparently retaining the effect of reagent vibrational excitation. The more-direct group (defined below) of trajectories does not exhibit this behavior. Reagent vibrational excitation does not increase the total rate coefficients for the title reaction more than the increase due to a simple temperature increase. The less-direct and more-direct groups of trajectories differ in their contribution to the rate coefficient for the title reaction. In particular, at T = 4000 K, the two PESs used in this work differ dramatically in the roles of the less-direct and more-direct trajectories. The behavior of the more-direct and less-direct groups of trajectories can be understood in terms of the efficiency of intramolecular vibrational energy transfer. This work utilizes the recently introduced PES Library, POTLIB 2001, which made the comparisons between the two PESs discussed in this work possible in a very straightforward way.
Duchovic
Ronald J
RJ
Department of Chemistry, Indiana University Purdue University at Fort Wayne, Fort Wayne, Indiana 46805-1499, USA. duchovic@ipfw.edu
Parker
Marla A
MA