Abstract
The photoionization dynamics of rotationally hot molecular nitrogen are studied employing resonance enhanced multiphoton ionization in combination with photoelectron spectroscopy. Photodissociation of N2O at ∼203 nm results in highly rotationally excited N2 fragments in X 1∑g+(N″,v″=0,1) states and O atoms in the excited D21 state. Photoelectron detection of the rotationally hot N2 states is performed by a two-photon excitation to the lowest a″ 1∑g+ Rydberg state followed by one-photon ionization. The large number of observed rotational levels, from N′=49 up to N′=94, results in improved rotational parameters for a″ 1∑g+ (v′=0). In addition, experimental and theoretical rotationally resolved photoelectron spectra of the a″ 1∑g+(v′=0,1;N′) state are presented. In these spectra only ΔN=N+−N′=even transitions are observed, with a dominant ΔN=0 peak and rather weak ΔN=±2 peaks. The one-photon ionization is dominated by ejection of electrons in p and f partial waves. The agreement between experimental and calculated spectra is excellent.
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