DYNAMICS OF SELECTED ROVIBRONIC EIGENSTATES IN THE V-SYSTEM OF CARBON-DISULFIDE (CS2)-C-12,13

The dynamics of individual eigenstates of carbon disulfide, (CS2)-C-12 and (CS2)-C-13, resulting from the interaction of rovibronic levels of the B-1(2) State with background states, have been investigated in the lowest vibronic state 10V. Using time-resolved spectroscopy with FTL nanosecond laser pulses of jet-cooled molecules, eigenstate absorption intensities, linewidths gamma = 1/tau = (0.6-6.0) x 10(5) s(-1), and magnetic properties were determined, with the latter measured by Lande g factors of up to 0.04 in (CS2)-C-12 and hyperfine splittings of up to 10 MHz in (CS2)-C-13. The intensities and linewidths were found to be linearly correlated in sets of eigenstates of a rovibronic level. This behaviour revealed the background states to be essentially dark, allowing us to estimate the linewidths of the zero-order states. Hyperfine splittings and g factors show no simple correlation with the intensity, a finding which is attributed to the second-order origin of the background state magnetic properties. Based on the density and the characteristics of the eigenstates, a coupling scheme is proposed, for which the background states represent rovibronic levels of the B-evs(2) spin component of the (3)A(2) electronic state interacting with highly excited rovibronic levels of the 1 Sigma(g)(+) electronic ground state.