Molecular multiphoton ionization spectroscopy.
Multiphoton ionization (MPI) spectroscopy is rapidly evolving into a valuable adjunct to VUV spectroscopy for the study of the highly excited states of molecules. The technique is described, and several examples are given of its applications. Studies of the 3p(z) Rydberg states of the methylbenzenes and of the (1)B(2u) state of benzene show that state assignments can be made and new multiphoton structure seen that is not available in one-photon spectra. MPI of benzene in a supersonic jet demonstrates dramatic resolution improvement and shows that natural linewidth information can be gained for large molecules. Collisional effects in MPI spectra are briefly discussed with reference to Xe and to laser enhanced collisional broadening of nitric oxide in the supersonic beam.
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Johnson