Time-Resolved Coincidence Imaging of Multiphoton-Induced Dynamics in CS₂⁺

We report time-resolved coincidence momentum imaging of photo-induced dynamics in gas-phase CS₂ using a COLTRIMS reaction microscope with a 396 nm pump and a 780 nm probe. By exploiting full vector-momentum correlations, we disentangle multiple excitation and fragmentation pathways that are otherwise strongly overlapped in ion spectra, providing a new view of the complex dynamics dominated by CS₂⁺ manifold evolution. We observe prompt C–S bond–cleavage channels that exhibit a rapidly emerging dissociation feature in the two-body kinetic-energy release as a function of pump–probe delay. In contrast, the central-atom-elimination channel yielding S₂⁺ appears with a clear delay relative to the prompt C–S breakup channels, consistent with a structural rearrangement preceding S–S bond formation in the ionic state following six-photon absorption. In addition, the delay dependence of three-body channels reveals a transient bending wave packet, suggesting bending motion could be a precursor coordinate that seeds fragmentation. These measurements demonstrate a route to isolate distinct dynamical pathways in a prototypical triatomic molecule and motivate wave-packet-control experiments.