The triplet channel in the photodissociation of ozone in the Hartley band: Classical trajectory surface hopping analysis

The triplet channel in the photodissociation of ozone in the Hartley band, O-3+hv -> O(P-3) +O-2 ((3)Sigma), is investigated by means of a classical trajectory surface hopping method using ab initio diabatic potential energy surfaces for the B and the R states. Because of the strong recoil in the R state along the breaking O-O bond, O-2((3)Sigma) is produced with a high rotational energy. The nonadiabatic transition probability depends markedly on the coordinate along the crossing seam. As a consequence a unique correlation is found between the internuclear geometry at the crossing and the final vibrational state of O-2((3)Sigma). The calculated distribution of the translational energy is in good accord with the measured distribution. (c) 2005 American Institute of Physics.