Recoil-induced vibrational excitation in inner-shell photoelectron spectra: Beyond the linear coupling model

T. Darrah Thomas, Kiyoshi Ueda

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)


The interplay between Franck-Condon and recoil-induced vibrational excitation in core-electron photoionization has been investigated using generalized Franck-Condon factors. Three models for the vibrational wave functions have been considered: the linear-coupling model, the harmonic oscillator, and the Morse oscillator. At every level it appears that the two processes can be treated as independent, and the total vibrational excitation energy is simply the sum of the excitation energies characteristic of the two processes. At the level of the linear coupling model, the vibrational excitation profile is exactly the convolution of the profiles for the two different processes; for the other levels of approximation the overall profile differs only slightly from the convolution. The results also show that the vibrational intensity ratio, Rv=(v=1)/(v=0), varies linearly with the vibrational excitation, but that the proportionality constant relating these two quantities is not h ω2, as has been previously assumed, but h ω1 (where ω1 and ω2 are the characteristic vibrational frequencies of the neutral and ionized molecules, respectively).

Original languageEnglish
Pages (from-to)101-108
Number of pages8
JournalJournal of Electron Spectroscopy and Related Phenomena
Publication statusPublished - 2014 Aug


  • Effect of anharmonicity
  • Inner-shell ionization
  • Recoil excitation

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Radiation
  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Spectroscopy
  • Physical and Theoretical Chemistry


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