Reactions of Hydrated Electrons (H2O)n− with Carbon Dioxide and Molecular Oxygen: Hydration of the CO2− and O2− Ions

✍ Scribed by O. Petru Balaj; Chi-Kit Siu; Iulia Balteanu; Martin K. Beyer; Vladimir E. Bondybey

• Publisher: John Wiley and Sons
• Year: 2004
• Tongue: English
• Weight: 269 KB
• Volume: 10
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.200400416

✦ Synopsis

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 CO~2~ and O~2~ react efficiently with (H~2~O)~n~^−^ because they possess low‐lying empty π* orbitals. The molecular CO~2~^−^ and O~2~^−^ anions are concurrently solvated and stabilized by the water ligands to form CO~2~^−^(H~2~O)~n~ and O~2~^−^(H~2~O)~n~. Core exchange reactions are also observed, in which CO~2~^−^(H~2~O)~n~ is transformed into O~2~^−^(H~2~O)~n~ upon collision with O~2~. This is in agreement with the prediction based on density functional theory calculations that O~2~^−^(H~2~O)~n~ clusters are thermodynamically favored with respect to CO~2~^−^(H~2~O)~n~. Electron detachment from the product species is only observed for CO~2~^−^(H~2~O)~2~, in agreement with the calculated electron affinities and solvation energies.