Application of the time-dependent wavepacket method to mass spectrometric studies of molecular excitation and dissociation

A new time-dependent wavepacket approach has been applied to illustrate a rigorous method of calculating the transition function for bound-to-continuum transitions in translational energy spectrometric experiments. The method is numerically exact and fully quantal, and is devoid of any classical or semi-classical approximations. The validity of the hitherto-applied reflection approximation is investigated in a comparative study. The method has been applied to two different translational energy spectrometry experiments: collision-induced dissociation of CO + and collisional excitation of H 2 .