Vibrational and rotational decoupling approximations are tested in three-dimensional Fermi Golden Rule calculations on energies, lifetimes, and product state distributions of the vibrationally predissociating atom-diatom van der Waals complexes. The validity of approximate separations of diatom vibration, decoupling of stretching and bending intermolecular motions, and rotational infinite order sudden approximation for product scattering is characterized by comparison with the results of accurate calculations on the Ne⋯Cl2, Ne⋯ICI, and He ⋯ ICI systems. The most accurate approximate schemes are recommended.
|Number of pages||12|
|Journal||Journal of Computational Chemistry|
|Publication status||Published - Jun 1996|