Electron-driven chemistry of halogenated compounds in condensed phases: Effects of solvent matrices on reaction dynamics and kinetics

The focus of this review is the effect of H2O on the electron-driven chemistry of condensed halogenated compounds. We present data with emphasis on results from the authors’ laboratories for halomethanes (CF2Cl2, CCl4, CH3I, CDCl3, CD2Cl2) and SF6. The halogenated species are suspended in or adsorbed on the surface of ultrathin films of amorphous solid water (ice) condensed on metal surfaces. Bombardment of the film by X-rays or energetic electrons leads to the release of low-energy secondary electrons; these are responsible for much of the rich electron-driven chemistry, which includes molecular decomposition, desorption of charged and neutral fragments, radical formation, anion solvation, and condensed-phase reactions. Potential implications of this work range from environmental remediation of toxic compounds to atmospheric ozone depletion.