Model study on the real-time detection of ultrafast nonadiabatic dynamics associated with the Wulf-Chappuis bands of ozone

Model calculations on the cw absorption spectrum and femtosecond time-resolved stimulated-emission pump-probe spectra are reported for the Wulf-Chappuis bands of ozone. The model accounts for the three dimensional conical intersection of the ¹A₂ and ¹B₁ excited states and the associated singular non-Born-Oppenheimer coupling. Effects of dissociation into O+O₂ are modelled phenomenologically. It is demonstrated on the basis of this model that detailed information on the ultrafast nonadiabatic excited-state dynamics can be obtained by pump-probe spectroscopy with ultrashort pulses (pulse duration of the order of 10 fs).