title: Regular vibrational state progressions at the dissociation limit of SCCl2.
abstract: We observe sharp features in the vibrational spectrum of SCCl(2) at and above its two lowest-lying dissociation limits. Highly regular vibrational progressions persist at dissociation, as in some smaller molecules studied previously by others. Nearly all of the SCCl(2) transitions studied by stimulated emission pumping can be assigned and fitted by a simple effective Hamiltonian without resonance terms, up to a total vibrational excitation of 36 quanta. The character of the highly excited vibrational wave functions is not normal mode-like, but it nonetheless arises gradually from the normal modes as the energy increases. The number of sharp vibrational features observed matches a scaling model that predicts localization of nearly all vibrational states near dissociation as the size of a polyatomic molecule increases.
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign, Illinois 61801, USA.
authors.forename: Praveen D
authors.initials: PD
authors.lastname: Chowdary
authors.forename: Martin
authors.initials: M
authors.lastname: Gruebele