A theoretical approach toi the O(~1D)+H_2O(X~1A_1)reaction:Ab initio potential energy surface and quasiclassical trajiectory dynamics study

摘要

An ab initio study of the ground potential energy surface (PBS) of the O( 1D) ± H20 system has been performed, employing M0ller—Plesset methods. From the stationary and additional points calculated, the ground PBS has been modeled as a triatomic system, with an OH group of the H20 molecule treated as a single atom of 17.0 amu. The rate constant of reaction (1), O( ‘D) ± H20—QOH (main reaction channel), estimated from the quasiclassical trajectory (QCT) calculations is reasonably close to the recommended experimental value. For the relative translational energies explored (ET~ 0.234, 0.303, and 0.443 eV) and H20 at T~ 300 K, the QCT OH vibrational populations are in good agreement with the experimental values reported for the new OH fragment, but the QCT OH average rotational energies are in general quite larger than the experimental ones. Regarding the stereodynamics, for ET 0.234 eV there is not a clear tendency to a particular rotational alignment of the OH product with respect to the initial relative velocity vector, in agreement with experiments. The QCT results also show that nearly all reactive trajectories leading to reaction (1) take place through an insertion microscopic mechanism, which, even at the highest ET value considered (0.443 eV), is mainly (70%) a nondirect one. The collision complex has an average lifetime of about three rotational periods and a geometry around that of the HO(OH) hydrogen peroxide molecule. The QCT results concerning the microscopic mechanism of reaction (1) are in agreement with the suggested ones by the experimentalists to interpret their results. The present study should be considered as a starting point in the study of reaction (1) from which different aspects on the dynamics may be learned.