Coupled channel golden-rule quantum mechanical calculations of total and partial decay widths are reported for vibrational predissociation of HF dimer. In this calculation, an ab initio potential energy surface is employed in both bound and scattering calculations but the vibrational coupling is given by an electrostatic interaction. The computed lifetime of HF dimer is 4.0 and 4.8 ns for v2+ and v2- ("bound- H") excitation, and 11 ns for both v1+ and v1- ("free-H") excitations. These theoretical lifetimes are compared to the experimental values of about 1 ns for the v2 excitation and about 20 ns for the v1 excitation. We also present rotational state distributions of HF monomers which are in qualitative agreement with the experimental measurement of Bohac et al. [J. Chem. Phys. 96, 6681 (1992)].
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry