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Keywords:

  • gas-phase reactions;
  • hydrated electrons;
  • nanodroplets;
  • radical ions;
  • solvation

Abstract

The gas-phase reactions of hydrated electrons with carbon dioxide and molecular oxygen were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Both CO2 and O2 react efficiently with (H2O)n because they possess low-lying empty π* orbitals. The molecular CO2 and O2 anions are concurrently solvated and stabilized by the water ligands to form CO2(H2O)n and O2(H2O)n. Core exchange reactions are also observed, in which CO2(H2O)n is transformed into O2(H2O)n upon collision with O2. This is in agreement with the prediction based on density functional theory calculations that O2(H2O)n clusters are thermodynamically favored with respect to CO2(H2O)n. Electron detachment from the product species is only observed for CO2(H2O)2, in agreement with the calculated electron affinities and solvation energies.