On the coupling in the final state in the photoelectron spectra

Abstract

The coupling in the state e+AB ⁺ for the He I photoelectron spectra is considered by explicit calculation of the appropriate S ^† matrix elements. Coulomb functions are taken for the asymptotic states and the additional interaction is approximated by an electrostatic multipole expansion. A fixed body frame treatment is used. The coupling S ^† elements are given, to first and second order, by multipole integrals and differ according to the change in electronic state energy and R dependence involved. In the approximation used the symmetry (i.e. Λ) of the electronic states remains the same. Vibrational effects are found to depend on whether the identical or different electronic potential curves occur in the multipole matrix elements. Harmonic oscillator selection rules or the displaced oscillator integrals, respectively, determine the extent of the coupling in these two cases. A sample computation is presented for the N₂+(X ²Σ_g) state.

Based in part on work done while at the Department of Chemistry, University of California, Irvine, U.S.A.

Based in part on work done while at the Department of Chemistry, University of California, Irvine, U.S.A.

Notes

Based in part on work done while at the Department of Chemistry, University of California, Irvine, U.S.A.