On-the-fly ab initio trajectory calculations of the dynamics of Cl atom reactions with methane, ethane and methanol

The dynamics of Cl atom reactions with methane, ethane, and methanol have been studied by calculation of quasi-classical trajectories, with computation of potential energies and gradients only at the geometries through which the trajectories pass. Trajectories were started from the transition state, with 2 kcal mol(-1) of energy given to the mode with an imaginary frequency (representing the reaction coordinate at the transition state) and inclusion of zero-point energy in some or all of the remaining vibrational modes. The trajectories were propagated as far as separated products, with the majority of potential energy calculations performed at the HF/6-31G level of theory. The rotational quantum state population distributions of the HCl products from the reactions of Cl atoms with methane, ethane and methanol peaked at J'=1, 2, and 6, respectively. The calculations thereby exhibit somewhat greater rotational excitation than is found experimentally, but correctly describe the trend of increasing HCl product rotation for the three respective reactions. In agreement with previous observations, only 4% of the energy available to the products of the reaction of Cl atoms with methane was channeled into CH3 radical internal energy, and 1% into HCl rotation, with 92% ending up as translational energy. For the reaction of Cl atoms with ethane and with methanol, the corresponding values for radical internal energy, HCl rotation and product translation are 21, 3, and 78%, and 46, 13, and 42%, respectively. For the latter two reactions, the radical internal energy is mostly accounted for by rotational motion. The clear increase in rotational excitation of the HCl products from the Cl atom reaction with methanol is explained in terms of a dipole-dipole interaction between the departing polar fragments. A smaller set of more computationally expensive trajectory calculations using potentials and gradients from the MP2/6-311G(d,p) level of theory were performed for reactions of Cl atoms with methanol, and give results in better agreement with experimentally measured HCl rotational excitation, consistent with the model of dipole-induced product rotation because the MP2/6-311G(d,p) calculations give smaller dipole moments for both products than the HF/6-31G calculations. The calculated angles between the rotational angular momentum vectors and recoil velocities of the radical peak sharply at 90 degrees for the reactions of Cl atoms with ethane and methanol, but exhibit a much broader distribution for reaction with methane.