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Updated: Apr 7, 2026

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−
Published on: July 27, 2018
Probing keto-enol tautomerism using photoelectron spectroscopy
Nathalie Capron1, Bastien Casier, Nicolas Sisourat
1Sorbonne Universités, UPMC Univ Paris 06, UMR 7614, Laboratoire de Chimie Physique Matière et Rayonnement, F-75005, Paris, France. Nicolas.Sisourat@upmc.fr.
Abstract:
We theoretically investigate the mechanism of tautomerism in the gas-phase acetylacetone molecule. The minimum energy path between the enolone and diketo forms has been computed using the Nudged-Elastic Band (NEB) method within the density-functional theory (DFT) using the projector augmented-wave method and generalized gradient approximation in Perdew-Wang (PW91) parametrization. The lowest transition state as well as several intermediate geometries between the two stable tautomers have been identified. The outer-valence ionization spectra for all determined geometries have been computed using the third-order non-Dyson algebraic diagrammatic construction technique. Furthermore, the oxygen core-shell ionization spectra for these geometries have been obtained using DFT and the Becke three-parameter Lee-Yang-Parr (B3LYP) functional. It is shown that all spectra depend strongly on the geometries demonstrating the possibility of following the proton-transfer dynamics using photoelectron spectroscopy in pump-probe experiments.
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