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Title: Communication: Remarkable electrophilicity of the oxalic acid monomer: An anion photoelectron spectroscopy and theoretical study

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:
; ; ;  [1] ; ;  [2] ;  [2] ;  [3] ;  [4]
  1. Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218 (United States)
  2. Institute of Chemical Sciences, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh, Scotland, EH14 4AS (United Kingdom)
  3. (Botswana)
  4. Computational Research Division, Lawrence Berkeley National Laboratory, One Cyclotron Road, MS 50F-1650, Berkeley, California 94720 (United States)
Publication Date:
OSTI Identifier:
22420081
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 22; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANIONS; BONDING; CARBON; ELECTRONS; INTERACTIONS; MOLECULAR ORBITAL METHOD; MONOMERS; OXALIC ACID; PHOTOELECTRON SPECTROSCOPY