Does the radical Me3O center dot exist in the gas phase? A joint experimental and theoretical study

Abstract

A combination of experiment and theory indicate that when Me 3O+ undergoes vertical Franck-Condon one-electron reduction, it does not produce a stable Me3O• species, but decomposes to give MeOMe and Me•. Theoretical calculations at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-311G(d) level of theory indicate that the symmetrical radical Me3O• is not a stable species. However, there is a stable doublet neutral corresponding to a van der Waals complex MeOMe⋯Me, a species which requires only 4.5kJmol-1 of excess energy to cause decomposition to MeOMe and Me•. © 2003 Elsevier B.V. All rights reserved.