A time-dependent quantum dynamical study of the H+HBr reaction

Time-dependent wave packet calculations were carried out to stud, the exchange and abstraction processes in the title reaction on the Kurosaki-Takayanagi potential energy surface (Kurosaki, Y.; Takayanagi, T. J. Chem. Phys. 2003, 119, 7838). Total reaction probabilities and integral cross sections were calculated for the reactant HBr initially in the ground state, first rotationally excited state, and first vibrationally excited state for both the exchange and abstraction reactions. At low collision energy, only the abstraction reaction occurs because of its low barrier height. Once the collision energy exceeds the barrier height of the exchange reaction, the exchange process quickly becomes the dominant process presumably due to its larger acceptance cone. It is found that initial vibrational excitation of HBr enhances both processes, while initial rotational excitation of HBr from j(0) = 0 to 1 has essentially no effect on both processes. For the abstraction reaction, the theoretical cross section at E, = 1.6 eV is 1.06 angstrom(2), which is smaller than the experimental result of 3 +/- 1 angstrom(2) by a factor of 2-3. On the other hand, the theoretical rate constant is larger than the experimental results by about a factor of 2 in the temperature region between 220 and 550 K. It is also found that the present quantum rate constant is larger than the TST result by a factor of 2 at 200 K. However, the agreement between the present quantum rate constant and the TST result improves as the temperature increases.