ISSN:
0030-493X
Keywords:
Chemistry
;
Analytical Chemistry and Spectroscopy
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Cluster ions from fast atom bombardment of liquid alcohols and nitriles were examined using a continuous-flow technique. Protonated molecular MnH+ species are the dominant cluster ions observed in molecules of formula M. The abundances of the MnH+ cluster ions decrease monotonically with increasing n, and within a homologous series the MnH+ abundance diminishes more rapidly for higher molecular mass compounds. Reaction products (ROH)n(H2O)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.
Additional Material:
17 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/oms.1210280522
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