Photoelectron Photoion Coincidence Spectroscopy of Biradicals

The electronic structure of biradicals is characterized by the presence of two unpaired electrons in degenerate or near-degenerate molecular orbitals. In particular, some of the most relevant species are highly reactive, difficult to generate cleanly and can only be studied in the gas phase or in matrices. Unveiling their electronic structure is, however, of paramount interest to understand their chemistry. Photoelectron photoion coincidence (PEPICO) spectroscopy is an excellent approach to explore the electronic states of biradicals, because it enables a direct correlation between the detected ions and electrons. This permits to extract unique vibrationally resolved photoion mass-selected threshold photoelectron spectra (ms-TPES) to obtain insight in the electronic structure of both the neutral and the cation. In this review we highlight most recent advances on the spectroscopy of biradicals and biradicaloids, utilizing PEPICO spectroscopy and vacuum ultraviolet (VUV) synchrotron radiation.

Automated summary

The electronic structure of biradicals, which have two unpaired electrons in degenerate or near-degenerate molecular orbitals, is of great interest in understanding their chemistry. However, the study of these highly reactive species is challenging, as they are difficult to generate cleanly and can only be studied in specific conditions. Recent advances in photoelectron photoion coincidence (PEPICO) spectroscopy and vacuum ultraviolet (VUV) synchrotron radiation have provided valuable insights into the electronic structure of biradicals and biradicaloids.