Two-photon accessible Xe2 Rydberg states between its first two ionization limits

Two-photon resonance enhanced multiphoton ionization (REMPI) spectra of Xe2 transitions have been recorded in the wave number range between 92 500 and 94 780 cm−1 using time-of-flight (TOF) – mass spectrometry for ion detection. Seven new molecular excited states have been located between the first and second ionization limits of the dimer. Four of them are vibrationally resolved. Despite severe spectral congestion, separation and partial electronic symmetry assignments could be deduced from polarization measurements. Photoelectron spectra show that all observed molecular states in this region are strongly autoionized.