Novel radical anions and hydrogen atom tunneling in the solid state

Abstract

The radical anions and radical-anion pairs formed from the ..gamma.. or X radiation at low temperatures of acetonitrile, methyl halides, and dimethyl sulfoxide are characterized, and the chemical significance of the formation is discussed. ESR measurements of the spin distribution in the products produced by irradiation allow a fairly sharp distinction to be made in the anion form. Dimer radical anions were also found to be formed, but the crystal structure played a part in this process. Some of the radical anions were noted to undergo photolysis to give radical-anion pairs, which revert back to the original form via a thermal process. A competing reaction in which the radical abstracts a hydrogen atom from the neighboring molecule complicates the chemistry of the reversible process.