Electron Impact Catalytic Dissociation: Two-Bond Breaking by a Low-Energy Catalytic Electron

Authors

  • Dr. Daly Davis,

    1. Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, 69120 Heidelberg (Germany), Fax: (+49) 6221-54-5221
    Search for more papers by this author
  • Victor P. Vysotskiy,

    1. Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, 69120 Heidelberg (Germany), Fax: (+49) 6221-54-5221
    Search for more papers by this author
  • Dr. Y. Sajeev,

    Corresponding author
    1. Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, 69120 Heidelberg (Germany), Fax: (+49) 6221-54-5221
    • Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, 69120 Heidelberg (Germany), Fax: (+49) 6221-54-5221
    Search for more papers by this author
  • Prof. Dr. Lorenz S. Cederbaum

    Corresponding author
    1. Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, 69120 Heidelberg (Germany), Fax: (+49) 6221-54-5221
    • Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, 69120 Heidelberg (Germany), Fax: (+49) 6221-54-5221
    Search for more papers by this author

  • Financial support by the DFG (L.S.C.) and by the Alexander von Humboldt-Stiftung (Y.S.) is acknowledged. We would also like to acknowledge the reviewers for their remarks about the WH rules and DNA repair mechanism.

Abstract

original image

Upon impact of a low-energy electron on a neutral molecule, an intermediate metastable electron–molecule compound is formed. This species can undergo electron-catalyzed two-bond breaking or cycloelimination, as in the simplest case of the cyclobutane–ethylene conversion (see scheme). This mechanism is illustrated for the quadricyclanone–norbornadienone cycloelimination reaction using ab initio methods, and its generality appears promising.

Ancillary