Ultracold collisions of O(~1D) and H_2: The effects of H_2 vibrational excitation on the production of vibrationally and rotationally excited OH

摘要

A quantum dynamics study of the O(~1D) H_2(v=0 - 2, j 0) system has been carried out using the potential energy surfaces of Dobbyn and Knowles [Mol. Phys. 91, 1107 (1997)10.1080/002689797170842]. A time-independent quantum mechanical method based on hyperspherical coordinates is adopted for the dynamics calculations. Energy dependent cross section, probability, and rate coefficients are computed for the elastic, inelastic, and reactive channels over collision energies ranging from the ultracold to thermal regimes and for total angular momentum quantum number J =0. The effect of initial vibrational excitation of the H_2 molecule on vibrational and rotational populations of the OH product is investigated as a function of the collision energy. Comparison of results for vibrational levels v=0 - 2 of H_2 demonstrates that the vibrational excitation of H_2 and its non-reactive relaxation pathway play a minor role in the overall collisional outcome of O(~1D) and H_2. It is also found that while the state-resolved product vibrational distributions are sensitive to the initial collision energy and H_2 vibrational level, the product rotational distribution depicts an inverted population that is largely insensitive to initial conditions. Rate coefficients evaluated using a J-shifting approximation show reasonable agreement with available theoretical and experimental results suggesting that the J-shifting approximation may be used to evaluate the rate coefficients for O(~1D) H_2 reaction.