Triplet State Interrogation in Supersonic Beams by Surface Electron Ejection

Recently, we have developed an experimental method for the detection of triplet states generated by laser excitation in supersonic beams. It is based on electron ejection from low work‐function surfaces by metastable triplet states. We have detected both directly laser‐excited triplets and triplets generated via intersystem crossing from laser‐excited singlet states. Here, we review the applications of this method and discuss its mechanism. By comparing the laser‐induced fluorescence (LIF) spectrum and Surface Electron Ejection by Laser‐Excited Metastables (SEELEM), we have measured relative triplet formation quantum yields for several aromatic compounds. By utilizing a detector mounted on a translational stage, we could vary the distance between the pulsed laser excitation and the detector and measure the decay rates of triplets in molecular beams. The major advantage of the method is in extending the measurement of triplet lifetimes to the ∼ 1‐ms range. The combination of LIF, SEELEM, and fluorescence quantum yields enabled us to discriminate between intersystem crossing and internal conversion in isoquinoline. SEELEM is now being utilized in studying the spectroscopy and the dynamics of directly laser‐excited triplet states. Although the oscillator strength of the lowest triplet state of pyrazine is about 10⁻⁸, we have measured the spectrum and the decay rates of its various vibronic levels. Our results support the notion that surface Penning ionization is the mechanism of SEELEM. The detector is insensitive to vibrational energy (thus enabling the distinction between intersystem crossing and internal conversion). The detection sensitivity of triplets rises with the excess electronic energy and with the lowering of the surface work‐function.