A comparative study of the satellite structures in the photoelectron spectra of the Ne, Ar and Kr isoelectronic hydrides

Abstract

The satellite structures relative to the outer and inner valence ionizations of the Ne isoelectronic hydrides have been calculated employing the 3h-2v-1p configuration interaction (CI) scheme and the stability of the results for HF has been tested using the more extended 4h-3v-2p CI approach. The spectra obtained are well comparable with the experimental ones, allowing assignment for the various structures. These results and those previously obtained for the third and fourth row hydrides have been employed for a comprehensive analysis of the satellite structures in these molecules, aimed at a detailed examination of trends down the columns or across the rows. Although the satellites are dominated by similar effects, some different features are present because of the interplay of the quasidegenerate effects of the type found in the noble gases, and the interaction with the antibonding orbitais, which causes a considerable configuration mixing. Evidence is found for the minor importance of the outer valence satellites with respect to the inner valence ones in all molecules examined.