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

A combination of experiment and theory indicate that when Me₃O⁺ 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 MeOMeMe, a species which requires only 4.5 kJ mol⁻¹ of excess energy to cause decomposition to MeOMe and Me√.