Perpendicular vibrational predissociation of T-shaped van der Waals molecules

Abstract

In this paper we present a numerical quantum mechanical study for vibrational predissociation on a single electronic potential surface of a T-shaped van der Waals molecule B X⋅⋅⋅‖ C where X is a rare-gas atom while BC is a conventional diatomic molecule. The rare-gas atom is constrained to move on a line perpendicular to the interatomic axis of the BC molecule. The interaction between X and atoms B and C is represented by a sum of Morse atom–atom potentials. The close-coupling scattering equations were solved numerically and the vibrational predissociation rates were related to the widths of the resulting resonances. The method is applied to the HeI2 (B) van der Waals complex. We also present numerical results for the vibrational relaxation of linear X⋅⋅⋅B–C molecules where the three atoms are restricted to move on a single line. Good correspondence with the approximate (distorted wave) analytical results previously derived by us for ArI2, NeI2, and HeI2 is obtained.