Many-electron theory of x-ray photoelectron spectra: N-shell linewidths in the 46Pd to 92U range.

Abstract

The linewidths and energies of 4d holes (main lines in x-ray photoelectron spectra) are calculated for a number of elements in the range $_{70}\mathrm{Yb}$ to $_{92}\mathrm{U}$, with use of nonrelativistic atomic many-body theory. The nonrelativistic Hartree-Fock frozen-core approximation for one-electron wave functions and Auger energies gives very good agreement with experiment. In the case of 4s and 4p holes, the Auger (in particular, super-Coster-Kronig) energies have to be calculated with inclusion of relaxation and relativistic effects. Combined with frozen-core, nonrelativistic one-electron wave functions, this gives good agreement with experimental energies and widths for 4s and 4p holes in $_{80}\mathrm{Hg}$. In conclusion, it is very important to include the effects of two final-state holes on the Auger electron, as well as the polarization response which screens the Auger emission matrix element. This latter effect is largely equivalent to the so-called exchange interaction between the Auger electron and the final-state holes.