The role of the Coriolis interaction on vector correlations in molecular predissociation: Excitation of isolated rotational lines.

We present the full quantum mechanical expressions for the polarization differential cross sections of the photofragments produced in slow predissociation of a parent molecule via isolated rotational branches. Both radial and Coriolis nonadiabatic interactions between the molecular potential energy surfaces have been taken into account. The expressions describe the recoil angle distribution of the photofragments and the distributions of the photofragment angular momentum polarization (orientation and alignment) in terms of the anisotropy parameters of the ranks K=0,1,2. The explicit expressions for the anisotropy parameters are presented and analyzed which contain contributions from different possible photolysis mechanisms including incoherent, or coherent optical excitation of the parent molecule followed by the radial, or Coriolis nonadiabatic transitions to the dissociative states. The obtained expression for the zeroth-rank anisotropy parameter β is valid for any molecule and for an arbitrary value of the molecular total angular momentum J. The expressions for the orientation (K=1) and alignment (K=2) anisotropy parameters are given in the high-J limit in terms of the generalized dynamical functions which were analyzed for the case of photolysis of linear/diatomic molecules. As shown, the Coriolis nonadiabatic interaction results in several new photolysis mechanisms which can play an important role in the predissociation dynamics. [ABSTRACT FROM AUTHOR]