Vacuum ultraviolet photochemistry of sulfuric acid vapor: a combined experimental and theoretical study

Abstract

We present a vacuum ultraviolet (VUV) photoionization study of the gas-phase sulfuric acid (H₂SO₄) molecule in the 11–14 eV energy range by using the method of synchrotron radiation-based double imaging photoelectron photoion coincidence (i²PEPICO) spectroscopy complemented with accurate theoretical calculations. The slow photoelectron spectrum (SPES) of H₂SO₄ has been acquired and the three electronic states of H₂SO₄⁺, X²A, A²A and B²A have been populated and assigned. The adiabatic ionization energy of the H₂SO₄ molecule towards the X²A cationic ground state is measured at 11.684 ± 0.006 eV, in accordance with high-level calculated findings. With increasing photon energies, the H₂SO₄⁺ cation dissociates into HSO₃⁺ and OH fragments and their adiabatic appearance energy is measured at 13.498 ± 0.007 eV. Then, the enthalpies of formation for the species involved in the photoionization and dissociative photoionization have been determined through a thermochemical cycle.