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Dissociation of molecules by slow collisions with atoms

Alexander Z. Devdariani

Published Sep 1, 1975• 0 citations
OpenAlex

Abstract

The dissociation of molecules by collisions with excited atoms with the formation of an atom in an excited state is studied from the point of view of achieving population inversion in the atoms. (AIP)

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Processes involving a change of orbital angular momentum l and the dissociation of Rydberg molecules when they collide with inert-gas atoms are considered, using a method based on analyzing the terms of the interacting systems. The proposed method makes it possible to take into account the perturbations in a large group of Rydberg states that weakly penetrate into the ion core and to go beyond the limits of the two-level approximations [R. F. Stebbings and F. B. Dunning, eds., Rydberg States of Atoms and Molecules (Cambridge University Press, Cambridge, 1983; Mir, Moscow, 1985)] widely used in the theory of l mixing with the participation of Rydberg atoms. Using the Na**( nd )+Xe reaction as an example, it is demonstrated that this method gives good results in a wide range of variation of the principal quantum number n of the Rydberg electron ( n ≈10–40). Features of the l mixing and dissociation of Rydberg molecules are studied for the H 2 **+Xe system. It is shown that collisional dissociation occurs by the formation of an intermediate Rydberg state of the molecules, followed by self-decay into a dissociative continuum.
The formation of Li− by dissociative attachment in e+Li2 collisions is characterized by a large cross section for electron attachment to highly vibrationally excited Li2 molecules. However, the electronic structure of the Li−2 system dictates that low energy electrons (≲0.2 eV) are needed to minimize loss processes. An alternate production route for Li− is possible via direct ion‐pair formation through collisions of highly excited (Rydberg) Li atoms. The mechanisms for ion‐pair formation will be discussed in terms of the high‐lying molecular Rydberg states of Li2.