Threshold photoelectron spectroscopy of the HO₂ radical

We report a synchrotron radiation vacuum ultraviolet photoionization study of the hydroperoxyl radical (HO₂), a key reaction intermediate in combustion and atmospheric chemistry as well as astrochemistry, using double imaging photoelectron photoion coincidence spectroscopy. The HO₂ radical is formed in a microwave discharge flow tube reactor through a set of reactions initiated by F atoms in a CH₄/O₂/He gas mixture. The high-resolution threshold photoelectron spectrum of HO₂ in the 11 eV-12 eV energy range is acquired without interferences from other species and assigned with the aid of theoretically calculated adiabatic ionization energies (AIEs) and Franck-Condon factors. The three vibrational modes of the radical cation HO₂ ⁺, the H-O stretch, the H-O-O bend, and the O-O stretch, have been identified, and their individual frequencies are measured. In addition, the AIEs of the X³A″ ground state and the a¹A' first excited electronic state of HO₂ ⁺ are experimentally determined at 11.359 ± 0.003 eV and 11.639 ± 0.005 eV, respectively, in agreement with high-level theoretically computed results. Furthermore, the former AIE value provides validation of thermochemical networks used to extract the enthalpy of formation of the HO₂ radical.