title: Communication: Remarkable electrophilicity of the oxalic acid monomer: an anion photoelectron spectroscopy and theoretical study.
abstract: Our experimental and computational results demonstrate an unusual electrophilicity of oxalic acid, the simplest dicarboxylic acid. The monomer is characterized by an adiabatic electron affinity and electron vertical detachment energy of 0.72 and 1.08 eV (±0.05 eV), respectively. The electrophilicity results primarily from the bonding carbon-carbon interaction in the singly occupied molecular orbital of the anion, but it is further enhanced by intramolecular hydrogen bonds. The well-resolved structure in the photoelectron spectrum is reproduced theoretically, based on Franck-Condon factors for the vibronic anion → neutral transitions.
authors.affiliation: Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
authors.forename: Angela
authors.initials: A
authors.lastname: Buonaugurio
authors.affiliation: Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
authors.forename: Jacob
authors.initials: J
authors.lastname: Graham
authors.affiliation: Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
authors.forename: Allyson
authors.initials: A
authors.lastname: Buytendyk
authors.affiliation: Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
authors.forename: Kit H
authors.initials: KH
authors.lastname: Bowen
authors.affiliation: Institute of Chemical Sciences, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh, Scotland, EH14 4AS, United Kingdom.
authors.forename: Matthew R
authors.initials: MR
authors.lastname: Ryder
authors.affiliation: Institute of Chemical Sciences, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh, Scotland, EH14 4AS, United Kingdom.
authors.forename: Zibo G
authors.initials: ZG
authors.lastname: Keolopile
authors.affiliation: Computational Research Division, Lawrence Berkeley National Laboratory, One Cyclotron Road, MS 50F-1650, Berkeley, California 94720, USA.
authors.forename: Maciej
authors.initials: M
authors.lastname: Haranczyk
authors.affiliation: Institute of Chemical Sciences, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh, Scotland, EH14 4AS, United Kingdom.
authors.forename: Maciej
authors.initials: M
authors.lastname: Gutowski
mesh_terms: D000838:Anions / Q000737:chemistry*; D004583:Electrons; D006860:Hydrogen Bonding; D008962:Models, Theoretical; D019815:Oxalic Acid / Q000737:chemistry*; D056951:Photoelectron Spectroscopy; D011789:Quantum Theory
chemical_list: D000838:Anions; D019815:Oxalic Acid