R-matrix theory of electron molecule scattering

Abstract

This paper presents an overview of R-matrix theory of electron scattering by diatomic and polyatomic molecules. The paper commences with a detailed discussion of the fixed-nuclei approximation which in recent years has been used as the basis of the most accurate ab initio calculations. This discussion includes an overview of the computer codes which enable electron collisions with both diatomic and polyatomic molecules to be calculated. Nuclear motion including rotational and vibrational excitation and dissociation is then discussed. In non-resonant energy regions, or when the scattered electron energy is not close to thresholds, the adiabatic-nuclei approximation can be successfully used. However, when these conditions are not applicable, non-adiabatic R-matrix theory must be used and a detailed discussion of this theory is given. Finally, recent applications of the theory to treat electron scattering by polyatomic molecules are reviewed and a detailed comparison of R-matrix calculations and experimental measurements for water is presented.

Keywords:

• R-matrix theory
• Electron scattering
• Diatomic molecules
• Polyatomic molecules

Acknowledgement

The authors wish to acknowledge with thanks early discussions with Vic Saunders at the CCLRC Daresbury Laboratory when he gave them invaluable advice on the modification of molecular structure codes to treat electron molecule scattering using the R-matrix method.