Related Experiment Video
Updated: Apr 20, 2026

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−
Published on: July 27, 2018
Anion A(-) • HX clusters with reduced electron binding energies: proton vs hydrogen atom relocation upon electron
1Department of Chemistry, University of Minnesota , Minneapolis, Minnesota 55455, United States.
Abstract:
Clustering an anion with one or more neutral molecules is a stabilizing process that enhances the oxidation potential of the complex relative to the free ion. Several hydrogen bond clusters (i.e., A(-) • HX, where A(-) = H2PO4(-) and CF3CO2(-) and HX = MeOH, PhOH, and Me2NOH or Et2NOH) are examined by photoelectron spectroscopy and M06-2X and CCSD(T) computations. Remarkably, these species are experimentally found to have adiabatic detachment energies that are smaller than those for the free ion and reductions of 0.47 to 1.87 eV are predicted computationally. Hydrogen atom and proton transfers upon vertical photodetachment are two limiting extremes on the neutral surface in a continuum of mechanistic pathways that account for these results, and the whole gamut of possibilities are predicted to occur.
Related Concept Videos
Ionic Bonding and Electron Transfer
Electron Affinity
Aromatic Hydrocarbon Anions: Structural Overview
Due to the absence of continuous...
Ionization Energy
Ions and Ionic Charges
Molecular Structure and Acidity
The size effect explains the change in atomic size on acidity. When comparing the acids formed from elements that belong to the same column in the periodic table, their atomic sizes...

