Metastable Decomposition of {ROH}nH+ Cluster Ions (Where R = CH3 or CH3CH2)

We have studied the metastable decomposition of protonated alcohol cluster ions employing a reflectron time-of-flight mass spectrometer. Loss of a single alcohol molecule is observed as the dominant decomposition channel in all of these cluster ions. From the daughter ion spectra, we find experimental evidence that the {ROH} 6 H + cluster ions possess a unique stability relative to the parent cluster ion. Theoretical calculations were performed to interpret the cause for this special stability and to indicate several possible isomeric structures for this cluster ion. The energetic ordering of the isomers can be interpreted in terms of hydrogen bonding and delocalization of charge.