Proton transfer and isotope-induced reaction in aniline cluster ions.

ABSTRACT

The proton transfer (PT) and other intraclusters reactions occurring after electron ionization of aniline clusters (PhNH2)N are investigated by the time-of-flight mass spectrometry. The mass spectra are recorded for different expansion conditions leading to the generation of different cluster sizes. Several fragment ions are shown to originate from intracluster reactions, namely, [Ph](+), [PhNH3](+) and [Ph-N-Ph](+). Reaction schemes are proposed for these ions starting with the PT process. The mass region beyond the monomer mass is dominated by cluster ions (PhNH2)n(+) accompanied by satellites with ±H and +2H. In experiments with deuterated species, new fragment ions are identified. The aniline isotopomer d5-PhNH2 yields the fragment ions (PhNH2)n⋅(N-Ph-NH2)(+). Analogical series is observed in experiments with d7-PhND2, and additional fragments occur corresponding to (PhND2)n⋅(D2N-ND-Ph-ND-ND2)(+) ions. The possible reaction pathways to these ions and the unusual isotope effects are discussed.