Extreme ultraviolet laser/time-of-flight mass spectra of Kr2 near Kr*(4d,5p′,6s)

Abstract

New single-photon spectra of jet-cooled Kr2 between ∼98 700 and 99 900 cm−1 have been recorded with an extreme ultraviolet laser generated by four-wave sum-mixing in Xe gas. Molecular ions created by (1+1′) resonance enhanced multiphoton ionization, and daughter atomic ions created by excited state predissociation prior to ionization were mass dispersed and detected in a time-of-flight mass spectrometer. Analyses of the subsequent single isotopic spectra have resulted in vibrational numbering and constants for eight band systems of Kr2 that dissociate to Kr(1S0)+Kr*(4d,5p′,6s). Excited state bond lengths were estimated by Franck–Condon factor intensity simulations. When possible, electronic symmetry assignments for the states were established by correlation diagrams constructed from angular momentum arguments. Possible reasons are discussed for the deviations observed for the shape of many of the observed Rydberg state potential energy curves from their expected nonbonding form.