On the validity of the time-dependent self-consistent-field. approach: application to the vibrational predissociation of Cl2–Ne

The validity of the time-dependent self-consistent-field (TDSCF) approach assuming partial factorization of the wave packet is investigated. The TDSCF scheme is applied to a three-dimensional model of the Cl2–Ne vibrational predissociation, where only the bending mode is explicitly separated. The results are tested against previous exact and nearly exact calculations. A good agreement is found for the calculated predissociation lifetimes, but the method fails in the dynamical description of the factorized degree of freedom. The applicability and limitations of the approach are discussed.