Ionization of large homogeneous and heterogeneous clusters generated in acetylene-Ar expansions: cluster ion polymerization.

Pure acetylene and mixed Ar-acetylene clusters are formed in supersonic expansions of acetylene/argon mixtures and analysed using reflectron time-of-flight mass spectrometer with variable electron energy ionization source. Acetylene clusters composed of more than a hundred acetylene molecules are generated at the acetylene concentration of ≈8%, while mixed species are produced at low concentrations (≈0.7%). The electron energy dependence of the mass spectra revealed the ionization process mechanisms in clusters. The ionization above the threshold for acetylene molecule of 11.5 eV results in the main ionic fragment progression (C2H2)n(+). At the electron energies ≥21.5 eV above the CH+CH(+) dissociative ionization limit of acetylene the fragment ions nominally labelled as (C2H2)nCH(+), n ≥ 2, are observed. For n ≤ 7 these fragments correspond to covalently bound ionic structures as suggested by the observed strong dehydrogenation [(C2H2)n - k × H](+) and [(C2H2)nCH - k × H](+). The dehydrogenation is significantly reduced in the mixed clusters where evaporation of Ar instead of hydrogen can stabilize the nascent molecular ion. The C3H3(+) ion was previously assigned to originate from the benzene molecular ion; however, the low appearance energy of ≈13.7 eV indicates that a less rigid covalently bound structure of C6H6(+) ion must also be formed upon the acetylene cluster electron ionization. The appearance energy of Arn(C2H2)(+) fragments above ≈15.1 eV indicates that the argon ionization is the first step in the fragment ion production, and the appearance energy of Arn≥2(C2H2)m≥2(+) at ≈13.7 eV is discussed in terms of an exciton transfer mechanism.