Photoionization and photofragmentation in mass spectrometry with visible and UV lasers

Ever since the introduction of laser technology to the field of mass spectrometry, several disciplines evolved providing solutions to challenging scientific and analytical tasks in research and industry. Among these are techniques involving multiphoton ionization such as Resonance-Enhanced Multiphoton Ionization (REMPI, R2PI) and Mass-Analyzed Threshold Ionization (MATI) spectroscopy, a variant of Zero Kinetic Energy (ZEKE) spectroscopy, that possess the ability to selectively ionize certain preselected compounds out of complex mixtures, for example, environmental matrices, with a high level of efficiency. Another key feature of multiphoton ionization techniques is the ability to control the degree of fragmentation, whereas soft ionization is most highly appreciated in most applications. In cases where rich fragmentation patterns are desired for diagnostic purposes, Photodissociation mass spectrometry (PD-MS) is applied successfully. PD-MS allows for the cleavage of selected chemical bonds. With the introduction of chromophoric labels in PD-MS, it became possible to target certain molecules or groups within a molecule. In this review article, an overview of the basic principles and experimental requirements of REMPI and MATI spectroscopy and PD mass spectrometry are given. By means of selected examples, the latest developments and application possibilities in this field over the past decade with special focus on the German research landscape are pointed out. © 2018 Wiley Periodicals, Inc. Mass Spec Rev 38: 202-217, 2019.