Photodissociation spectroscopy via a rovibrational resonance in intense UV pulses

Photodissociation dynamics via a rovibrational resonance in intense UV pulses is investigated theoretically, using showcase ${\text{CH}}^{+}$ molecule promoted to the $\text{C}\phantom{\rule{0.16em}{0ex}}^{1}\mathrm{\ensuremath{\Sigma}}^{+}$ valence excited electronic state with potential barrier, thus giving access study shape controlled by pulse frequency. Simulations of kinetic energy release (KER) and angular distribution photofragments (ADP) spectra show dramatic differences for cases when tuned on off resonance. It shows that as increasing intensity transitions resonance, KER develop into new higher peaks overlying broadened background, which explained involvement other resonances partial waves through Rabi flopping between ground states. Those nonlinear contribution increases drastically probability photofragmentation along laser polarization ADP spectra. The coincident KER-ADP reveal clearly correlated vicinity dissociation barrier. present work opens possibilities manipulation ultrafast photodissociation help states continuum.