On the calculation of the satellite peaks observed in the high energy photoelectron spectra of small molecules

Abstract

The shake-up peaks which are observed to high binding energy of the main photoionization peak in the high energy photoeletron spectra of CO (carbon and oxygen core holes), H 2O and NH 3 have been interpreted by an extension of the singly excited configuration interaction method used previously in the study of the low-lying excited states of these molecules. The results obtained provide a good interpretation of the experimental spectra of these molecules in terms of many shake-up states. It is concluded that relaxed orbitals and an extensive basis set, including diffuse functions, should be used in the calculations in order to obtain good results.