Photoionisation and Auger Electron Emission from the Lithium Molecule: Calculations using Multicentre Numerical Continuum Functions

Abstract

A numerical method has been used for the generation of molecular continuum wavefunctions at the relaxed Hartree-Fock level associated with the photoionisation of the lithium molecule. Exchange between the continuum electron and the ion core is included, but L coupling is neglected. Cross sections for core and valence shell photoionisation have been calculated from threshold to 6·0 a. u. The results differ significantly in detail from previous multiple scattering calculations. Continuum phase shifts and the asymmetry parameters for the various processes are also reported. The molecular cross section values are compared with atomic cross sections calculated at the relaxed Hartree-Fock level. The Li2 molecular Auger transition rates are also calculated from first principles using the appropriate two-centre continuum functions. The results provide a basis for the reinterpretation of recent experimental findings of photoemission data for the lithium vapour system.