Journal of Physical Chemistry A, Vol.110, No.51, 13681-13685, 2006
Direct dynamics simulations of O(P-3)+HCl at hyperthermal collision energies
The dynamics of the O(P-3) + HCl reaction at hyperthermal collision energies were investigated using the quasiclassical trajectory method. Stationary points on the OClH (3)A' ' and (3)A' potential energy surfaces (PESs) were also examined. The lowest transition state leading to OCl + H on the (3)A' ' surface is 2.26 eV above the reagents at the CCSD(T)/cc-pVTZ level of theory. This saddle point is bent and product-like. Direct dynamics calculations at the MP2/cc-pVTZ level of theory were used to investigate the excitation functions for OH + Cl, OCl + H, and O + H + Cl formation. OCl is formed mainly from small-impact-parameter collisions, and the OCl + H excitation function peaks around 5 eV, where it is similar in magnitude to the OH + Cl excitation function. The shape of the OCl + H excitation function is discussed, and features are identified that should be general to hyperthermal collision dynamics.