Journal of Physical Chemistry A, Vol.112, No.13, 2762-2772, 2008
Effect of the excitation energy on the (HI)(2) nonadiabatic photodissociation dynamics
The effect of the excitation energy on the nonadiabatic photodissociation dynamics of (HI)(2) is explored in this work. A wave packet model is applied that simulates the photodissociation process starting from the I*-HI complex left behind after dissociation of the first III moiety within (HI)(2). The probability and product fragment state distributions of the different photodissociation pathways are analyzed in a wide range of excitation energies of the I*-HI absorption spectrum. It is found that the probability of electronically nonadiabatic transitions increases substantially.(by a factor larger than two) in the range of excitation energies analyzed. This increase is due to an enhancement of the intensity of the spin-rotation coupling responsible for the nonadiabatic transitions with increasing excitation energy. A remarkably high fraction of bound, highly excited I-2 photoproducts, slowly decreasing as the excitation energy increases, is also found over the range of energies studied. The I-2 product state distributions show manifestations of rotational interference effects and also of rotational cooline, in the case of the I-2 state distributions produced upon nonadiabatic transitions. Such effects become more pronounced with increasing energy. Experimental implications of these findings are discussed.