Organic cluster ions from continuous‐flow fast atom bombardment

Abstract

Abstract Cluster ions from fast atom bombardment of liquid alcohols and nitriles were examined using a continuous‐flow technique. Protonated molecular M n H + species are the dominant cluster ions observed in molecules of formula M. The abundances of the M n H + cluster ions decrease monotonically with increasing n , and within a homologous series the M n H + abundance diminishes more rapidly for higher molecular mass compounds. Reaction products (ROH) n (H 2 O)H + and (ROH) n (ROR)H + are observed also in the case of alcohols, and the ion abundances decrease with increasing n . Radiation damage yields fragment ions and ionic alkyl reaction products which are captured in solvent clusters. Semi‐empirical molecular orbital methods were used to examine the energetics of cluster ion formation and decomposition pathways. Metastable decomposition processes exhibit only evaporative loss of monomers, with the probability of loss increasing sharply with n . The evaporative ensemble model of Klots was used to predict the cluster size‐dependent trends of metastable dissociation processes observed for alcohol and nitrile cluster ions.