Intracluster ion-molecule reactions of the photoionized van der Waals complexes of C6H5F with NH3 and with H2O have been investigated by means of two-color multiphoton ionization spectroscopy in combination with mass analysis. Two different intracluster reactions of C6H5F-NH3, the substitution reaction yielding C6H5NH2+ and the dissociation yielding C6H5F+, were induced by the selective photoionization of different isomers of the complexes. Ionization threshold spectra 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 C6H5NH2+ production. Isomer-dependent reactions occurring within the H2O complexes were also presented, and their energetics was discussed in relation to a barrier height to the substitution reaction.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry