Accurate quantum mechanical calculations of differential and integral cross sections and rate constant for the O+OH reaction using an ab initio potential energy surface.
The authors report accurate quantum mechanical studies of the O+OH reaction on the improved Xu-Xie-Zhang-Lin-Guo potential energy surface. The differential cross section was obtained at several energies near the reaction threshold using a time-independent method. The dominant forward and backward peaks in the angular distribution are consistent with a complex-forming mechanism, which is also confirmed by the extensive rotational excitation in the O2 product. However, the asymmetry of these peaks suggests a significant nonstatistical component. The initial state (upsilon i=0, j i=0) specified integral cross section, which was calculated up to 1.15 eV of collision energy using the Chebyshev wave packet method, shows no energy threshold and decreases with the increasing collision energy, consistent with the barrierless nature of the reaction. The resulting rate constant exhibits a negative temperature dependence for T>100 K and decays as the temperature is lowered, in qualitative agreement with available experimental data.
Lin
Shi Ying
SY
Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.
Guo
Hua
H
Honvault
Pascal
P
Xu
Chuanxiu
C
Xie
Daiqian
D