General treatment for stereo-dynamics of state-to-state chemi-ionization reactions

Abstract

AbstractThe investigation of chemi-ionization processes provides unique information on how the reaction dynamics depend on the energy and structure of the transition state which relate to the symmetry, relative orientation of reagent/product valence electron orbitals, and selectivity of electronic rearrangements. Here we propose a theoretical approach to formulate the optical potential for Ne*(3P2,0) noble gas atom chemi-ionizations as prototype oxidation processes. We include the selective role of atomic alignment and of the electron transfer mechanism. The state-to-state reaction probability is evaluated and a unifying description of the main experimental findings is obtained. Further, we reproduce the results of recent and advanced molecular beam experiments with a state selected Ne* beam.The selective role of electronic rearrangements within the transition state, quantified through the use of suitable operative relations, could cast light on many other chemical processes more difficult to characterize.