Electronic recoil effects in high-energy photoelectron spectroscopy

W. Domcke, L. S. Cederbaum

Research output: Contribution to journalArticlepeer-review

71 Scopus citations

Abstract

It is shown that the recoil energy imparted to the residual ion by the outgoing fast photoelectron leads to noticeable modifications of X-ray excited photoelectron spectra of molecules containing light atoms. The vibrational band envelopes may differ considerably from those predicted by the Franck-Condon principle. AlKα excited valence electron bands are shown to exhibit, in addition to the translational recoil energy of the molecule, energy shifts of up to several tenth of an eV due to recoil-induced vibrational and rotational excitation. This effect has to be kept in mind when ionization potentials are determined from ESCA spectra. The recoil-induced vibrational and rotational excitation depends on the orbital quantum numbers of the ionized electron. Simple formulae for the shift of the centroid and the broadening of the band due to recoil effects are given for the special case of diatomic molecules.

Original languageEnglish
Pages (from-to)161-173
Number of pages13
JournalJournal of Electron Spectroscopy and Related Phenomena
Volume13
Issue number3
DOIs
StatePublished - 1978
Externally publishedYes

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