Chemical Physics Letters, Vol.318, No.6, 578-584, 2000
Blueshifts of the B <- X excitation spectra of (HeBr2)-Br-79 using a DIM-based potential
A first-order diatomics-in-molecule potential energy surface (PES) for the excited B state of the HeBr2 Van der Waals complex is implemented for the calculation of its B <-- X vibronic spectra at high vibrational excitations rr of the Br,(B) fragment. The parameters of the PES, which should describe true He-Br interactions, are determined empirically. It is found that three-body interactions included in the model markedly change the topological properties of the PES with respect to a simple pairwise one. In particular, they are responsible for the decrease of the frequency shift at upsilon > 33 observed experimentally. Better agreement with the experimental spectrum is also attained at very high vibrational excitations where the effects of intramolecular vibrational relaxation are essential.