Vibrational predissociation of highly vibrationally excited van der waals molecules: A quantal close‐coupling calculation

Abstract

AbstractIn this paper we present numerical calculations of close‐coupling equations to study vibrational predissociation of the T‐shaped He…︁I2(B) van der Waals molecule. In the region of high vibrational excitation of the I2 subunit, the vibrational predissociation rates are related to the widths of the resulting resonances for the He‐I2(B) collision. We apply a reasonable approximation to calculate the necessary background S matrix, i.e., the S matrix in absence of resonances. The rates of perpendicular vibrational predissociation, as a function of the initial I2 vibrational quantum number v1, show a maximum at v1 = 58 almost in agreement with the experimental data. However, an oscillatory and very interesting behavior of the rates in the region 60 ≤ v1 ≤ 65 is found.