Electron momentum spectroscopy of dimethyl ether taking account of nuclear dynamics in the electronic ground state

Filippo Morini, Noboru Watanabe, Masataka Kojima, Michael Simon Deleuze, Masahiko Takahashi

Research output: Contribution to journalArticlepeer-review

13 Citations (Scopus)

Abstract

The influence of nuclear dynamics in the electronic ground state on the (e,2e) momentum profiles of dimethyl ether has been analyzed using the harmonic analytical quantum mechanical and Born-Oppenheimer molecular dynamics approaches. In spite of fundamental methodological differences, results obtained with both approaches consistently demonstrate that molecular vibrations in the electronic ground state have a most appreciable influence on the momentum profiles associated to the 2b1, 6a1, 4b2, and 1a2 orbitals. Taking this influence into account considerably improves the agreement between theoretical and newly obtained experimental momentum profiles, with improved statistical accuracy. Both approaches point out in particular the most appreciable role which is played by a few specific molecular vibrations of A1, B1, and B2 symmetries, which correspond to C-H stretching and H-C-H bending modes. In line with the Herzberg-Teller principle, the influence of these molecular vibrations on the computed momentum profiles can be unraveled from considerations on the symmetry characteristics of orbitals and their energy spacing.

Original languageEnglish
Article number134309
JournalJournal of Chemical Physics
Volume143
Issue number13
DOIs
Publication statusPublished - 2015 Oct 7

ASJC Scopus subject areas

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

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