Laser multiphoton ionization of tetrakis(dimethylamino)ethylene.

The tetrakis(dimethylamino)ethylene (TDAE) molecule possesses the lowest known molecular ionization potential (<5.4 eV) and exhibits an intense Rydberg series between the first and second ionization limit (∼14 eV). The ionization of TDAE using multiphoton ionization photoelectron spectroscopy was carried out using laser light at a variety of wavelengths with a hemispherical energy analyzer. Interestingly, photoelectron signal due to direct two-photon ionization was not seen, rather ionization from a fluorescent charge-transfer state located ∼2.5 eV below the ionization limit was evident and in general agreement with a previous study. In addition, a second intense peak exists corresponding to thermal energy electrons. Measurements of the angular distribution for the electrons due to photoionization from the intermediate state are peaked along the electric field vector of the laser and the thermal electrons direction is independent of this angle. From this, we propose that the thermal peak is most likely due to thermionic emission initiated through excitation of a known long-lived Rydberg state at ∼6.5 eV. Alternately, we speculate that excitation leading to thermionic emission could result from a "collective" excitation mechanism.