Suppression of the methyl radical loss from acetone cation within (CH3COCH3)(n)CH3COCH3+ clusters

Abstract

We have investigated the photophysics of the acetone radical cation in the vacuum ultraviolet energy region by multiphoton ionization combined with time-of-flight mass spectrometry in a cluster beam. We have found that the loss of methyl radical from the acetone radical cations is remarkably suppressed at 10.5 eV when they are solvated by a few neutral acetone molecules. The cluster ion mass spectra obtained by nanosecond and picosecond laser pulses reveal that there are intermolecular processes, occurring in several tens of picoseconds, which are responsible for the survival of the acetone cations in clusters. This remarkable solvation effect on the yield of the methyl radical loss from the acetone Cation can be rationalized by the intracluster vibrational energy redistribution and the self-catalyzed enolization which compete with the methyl radical loss process.