Using Pump−Probe Fluorescence Depletion To Study the Rotationally Resolved Spectra and the J -Dependent Predissociation Rate of CS 2

By monitoring single vibronic level pump−probe fluorescence depletion, the rotationally resolved spectra of the 46 482 cm -1 band of CS 2 were recorded. The molecular constants are ν 0 = 46 481.51(11) cm -1, B = 0.098 09(24) cm -1, and D = 6.7(9.3) × 10 -8 cm -1 . The J -dependent predissociation rate was analyzed. At low J levels the predissociation rate is dominated by the energy separation and the coupling between the bound and the repulsive states, while at high J levels the rate is controlled by the tunneling through the barrier of the centrifugal potential.