Vibrational predissociation dynamics of the He79Br2 van der Waals molecule: A quantum mechanical study

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Abstract
The vibrational predissociation of the HeBr2 van der Waals complex is studied by means of both accurate and approximate three dimensional quantum mechanical calculations. Simple atom–atom potentials have been tested for matching experimental measurements at low Br2 vibrational excitations. The fragmentation dynamics when the bromine subunit is close to its B state dissociation limit is then explored and compared with experiments. For low to intermediate vibrational statesv, good agreement with most of the data (spectral shifts, lifetimes, average structures, average product energies) is achieved. The closing of the Δv=−1 channel at v=44 and the binding energy at that position are successfully reproduced, although calculated and experimental blueshifts and linewidths are not in such good accordance in the v≳38 range. For these high vexcitations, fragmentation cross sections exhibit complicated structures indicating strong interactions among different quasibound states. In addition, interesting threshold and intramolecular energy redistribution effects are predicted. The closing of the Δv=−1 channel is found to be a gradual process where different dynamical regimes can be investigated in detail.