title: Electrons Mediate the Gas-Phase Oxidation of Formic Acid with Ozone.
abstract: Gas-phase reactions of CO3 (.-) with formic acid are studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Signal loss indicates the release of a free electron, with the formation of neutral reaction products. This is corroborated by adding traces of SF6 to the reaction gas, which scavenges 38 % of the electrons. Quantum chemical calculations of the reaction potential energy surface provide a reaction path for the formation of neutral carbon dioxide and water as the thermochemically favored products. From the literature, it is known that free electrons in the troposphere attach to O2 , which in turn transfer the electron to O3 . O3 (.-) reacts with CO2 to form CO3 (.-) . The reaction reported here formally closes the catalytic cycle for the oxidation of formic acid with ozone, catalyzed by free electrons.
authors.affiliation: Institut für Ionenphysik und Angewandte Physik, Leopold-Franzens-Universität Innsbruck, Technikerstraße 25, 6020, Innsbruck, Austria.
authors.forename: Christian
authors.identifier: http://orcid.org/0000-0003-0493-820X
authors.initials: C
authors.lastname: van der Linde
authors.affiliation: Department of Biology and Chemistry, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon Tong, Hong Kong SAR, China.
authors.forename: Wai-Kit
authors.identifier: http://orcid.org/0000-0001-8649-1805
authors.initials: WK
authors.lastname: Tang
authors.affiliation: Department of Biology and Chemistry, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon Tong, Hong Kong SAR, China. chiksiu@cityu.edu.hk.
authors.forename: Chi-Kit
authors.identifier: http://orcid.org/0000-0002-1162-6899
authors.initials: CK
authors.lastname: Siu
authors.affiliation: Institut für Ionenphysik und Angewandte Physik, Leopold-Franzens-Universität Innsbruck, Technikerstraße 25, 6020, Innsbruck, Austria. martin.beyer@uibk.ac.at.
authors.forename: Martin K
authors.identifier: http://orcid.org/0000-0001-9373-9266
authors.initials: MK
authors.lastname: Beyer
keywords: electron; gas-phase reactions; radical ions; reaction mechanisms; reactive intermediates