Study of isomer-dependent reactions of organic molecular clusters

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Intracluster ion-molecule reactions of the photoionized van der Waals Complexes of C_6H_5F with NH_3 and with H_2O have been investigated by means of two-color multiphoton ionization spectroscopy in combination with mass analysis. Two different intracluster reactions of C_6H_5F-NH_3, the substitution reaction yielding C_6H_5NH_2^+ and the dissociation yielding C_6H_5F^+, were induced by the selective photoionization of different isomers of the complexes. Ionization threshold specra of the complexes and appearance energies of the reaction products were observed. Energetics of the reactions was discussed on the bases of the experimental results and the calculated geometries of the isomers. It was concluded that the nucleophilic substitution reaction is responsible for the C_6H_5NH_2^+ production. Isomer-dependent reactions occurring within the H_2O complexes were also presented, and their energetics was discussed in relation to a barrier height to the substitution reaction.