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Production of C2H4Cl+ by dissociative photoionization of weak molecular complexes in C2H4+HCl mixtures

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Zeitschrift für Physik D Atoms, Molecules and Clusters

Abstract

The photoionization efficiency (PIE) spectrum from 600 to 1200 Å for the production of the ion C2H4Cl+ by dissociative photoionization of the products of room-temperature jet expansions of a 1:4 mixture of C2H4 and HCl was measured at several nozzle pressures. The results were resolved into the PIE yield curve for the heterodimer process C2H4·HCl+hv→C2H4Cl++H+e. This reaction is necessarily characterized by a large change in geometry between neutral complex and ionic product. The observed spectrum exhibits an unusual and conspicuous peak at 15.2 eV that is characterized by a sharp cutoff to the high energy side. This feature points to the onset of strongly nonstatistical channels for the production of C2H4Cl+ at this energy such that product formation proceeds through very few states. The observed onset of C2H4Cl+ at 11.92±0.24 eV is 17±6 kcal mol−1 above the true threshold. An important conclusion is that at all energies above the onset the yield of dissociative ionization of the heterodimer to the cation C2H4Cl+ is determined by dynamical factors.

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Authors and Affiliations

  1. Department of Chemistry, University of New Mexico, 87131, Albuquerque, NM, USA

    E. A. Walters, D. L. Arneberg & C. J. Santandrea

  2. Chemistry Department, Brookhaven National Laboratory, 11973, Upton, NY, USA

    J. R. Grover & M. G. White

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  1. E. A. Walters
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  3. D. L. Arneberg
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  4. C. J. Santandrea
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  5. M. G. White
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Walters, E.A., Grover, J.R., Arneberg, D.L. et al. Production of C2H4Cl+ by dissociative photoionization of weak molecular complexes in C2H4+HCl mixtures. Z Phys D - Atoms, Molecules and Clusters 16, 283–292 (1990). https://doi.org/10.1007/BF01437532

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  • DOI: https://doi.org/10.1007/BF01437532

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