title: Energy-resolved collision-induced dissociation of peroxyformate anion: enthalpies of formation of peroxyformic acid and peroxyformyl radical.
abstract: We measure the oxygen-oxygen bond dissociation energy of the peroxyformate anion (HCO(3)(-)) using energy-resolved collision-induced dissociation with a guided ion beam tandem mass spectrometer. The analysis of the dissociation process from HCO(3)(-) ((1)A') to HCO(2)(-) ((1)A(2)) + O((3)P) requires consideration of the singlet-triplet crossing along the reaction path and of the competing OH(-) and O(2)H(-) product channels. The measured oxygen-oxygen bond dissociation energy is D(0)(HCO(2)(-)-O) = 1.30 ± 0.13 eV (126 ± 12 kJ/mol). This threshold energy measurement is used in thermochemical cycles to derive the enthalpies of formation for peroxyformic acid, Δ(f)H(0)(HCO(3)H) = -287 ± 19 kJ/mol, and peroxyformyl radical, Δ(f)H(0)(HCO(3)(•)) = -98 ± 12 kJ/mol. These values are in good agreement with computational energies.
authors.affiliation: Department of Chemistry, University of Nevada, Reno, Reno, Nevada 89557-0216, USA.
authors.forename: Alex A
authors.initials: AA
authors.lastname: Nickel
authors.forename: Jerry G
authors.initials: JG
authors.lastname: Lanorio
authors.forename: Kent M
authors.initials: KM
authors.lastname: Ervin
mesh_terms: D000838:Anions / Q000737:chemistry; D005561:Formates / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D011789:Quantum Theory; D053719:Tandem Mass Spectrometry; D013816:Thermodynamics
chemical_list: D000838:Anions; D005561:Formates; D005609:Free Radicals; C008817:peroxyformic acid