Photoelectron photoionization technique PEPICO

To date, by far the best quantitative studies of unimolecular dissociations of ions with a well-defined energy distribution have been those using the photoelectron photoionization technique (PEPICO). These reactions have been discussed in detail elsewhere, most notably by Baer. ... 

Photoionization always produces two species available for analysis the ion and the electron. By measuring both photoelectrons and photoions in coincidence, the kinetic electron may be assigned to its correlated parent ion partner, which may be identified by mass spectrometry. The extension of the photoelectron-photoion-coincidence (PEPICO) technique to the femtosecond time-resolved domain was shown to be very important for studies of dynamics in clusters [131, 132]. In these experiments, a simple yet efficient permanent magnet design magnetic bottle electron spectrometer was used for photoelectron... 

Combination of PES with mass spectrometry in a coincidence system leads to an extremely powerful technique called photoelectron-photoion coincidence (PEPICO) spectroscopy, which renders it possible to examine dissociations of energy-selected molecular ions. 

Several methods exist that allow the determination of the standard enthalpies of formation of the ionic species. The reader is referred to two recent rigorous and detailed chapters by Lias and Bartmess and Ervin. The vast majority of the experimental data reported here are obtained by means of Fourier transform ion cyclotron resonance spectroscopy (FT ICR), high-pressure mass spectrometry (HPMS), selected ion flow tube (SIFT), and pulsed-field ionization (PFI) techniques, particularly pulsed-field ionization photoelectron photoion coincidence (PFI-PEPICO). All these experimental techniques have been examined quite recently, respectively, by Marshall, Kebarle, B6hme," ° Ng" and Baer. These chapters appear in a single (remarkable) issue of the International Journal of Mass Spectrometry. An excellent independent discussion of the thermochemical data of ions, with a careful survey of these and other experimental methods, is given in Ref. 37. 

PFI-PEPICO pulsed field ionization photoelectron-photoion coincidence technique... 

Photoionization has a number of advantages over electron impact ionization, such as greater sensitivity and thresholds that are easier to define. In coincidence photoelectron techniques (e.g., photoelectron photoion coincidence spectroscopy, PEPICO, and threshold photoelectron photoion coincidence spectroscopy, TPEPICO), the photoelectron and the photoion formed in the ionization process are detected simultaneously, thus providing information on the nature and energies of the ionized products. ... 

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