Photoelectron spectrum of the pyridyl radical

Abstract

We report the photoelectron spectrum of the pyridyl radical (C₅H₄N), a species of interest in astrochemistry and combustion. The radicals were produced via hydrogen abstraction in a fluorine discharge and ionized with synchrotron radiation. Mass-selected slow photoelectron spectra of the products were obtained from photoelectron–photoion coincidence spectra. A Franck–Condon simulation based on computed geometries and vibrational frequencies identified contributions of the o- and p-pyridyl radicals. For the o-isomer an adiabatic ionisation energy of 7.70 eV was obtained, in excellent agreement with a computed value of 7.72 eV. The spectrum of o-pyridyl is characterized by a long progression in an in-plane bending mode and the N–C stretch that contains the radical site.