Valence photoelectron spectroscopy of N2 and CO: Recoil-induced rotational excitation, relative intensities, and atomic orbital composition of molecular orbitals

T. D. Thomas, E. Kukk, T. Ouchi, A. Yamada, H. Fukuzawa, K. Ueda, R. Püttner, I. Higuchi, Y. Tamenori, T. Asahina, N. Kuze, H. Kato, M. Hoshino, H. Tanaka, A. Lindblad, L. J. Sthre

Research output: Contribution to journalArticlepeer-review

12 Citations (Scopus)


Recoil-induced rotational excitation accompanying photoionization has been measured for the X, A, and B states of N+2 and CO+ over a range of photon energies from 60 to 900 eV. The mean recoil excitation increases linearly with the kinetic energy of the photoelectron, with slopes ranging from 0.73× 10-5 to 1.40× 10-5. These slopes are generally (but not completely) in accord with a simple model that treats the electrons as if they were emitted from isolated atoms. This treatment takes into account the atom from which the electron is emitted, the molecular-frame angular distribution of the electron, and the dependence of the photoelectron cross section on photon energy, on atomic identity, and on the type of atomic orbital from which the electron is ejected. These measurements thus provide a tool for investigating the atomic orbital composition of the molecular orbitals. Additional insight into this composition is obtained from the relative intensities of the various photolines in the spectrum and their variation with photon energy. Although there are some discrepancies between the predictions of the model and the observations, many of these can be understood qualitatively from a comparison of atomic and molecular wavefunctions. A quantum-mechanical treatment of recoil-induced excitation predicts an oscillatory variation with photon energy of the excitation. However, the predicted oscillations are small compared with the uncertainties in the data, and, as a result, the currently available results cannot provide confirmation of the quantum-mechanical theory.

Original languageEnglish
Article number174312
JournalJournal of Chemical Physics
Issue number17
Publication statusPublished - 2010 Nov 7

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry


Dive into the research topics of 'Valence photoelectron spectroscopy of N<sub>2</sub> and CO: Recoil-induced rotational excitation, relative intensities, and atomic orbital composition of molecular orbitals'. Together they form a unique fingerprint.

Cite this