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.

We report an electron momentum spectroscopy study of vibrational effects on the electron momentum distributions of the outer valence orbitals of adamantane (C 10 H 16). The symmetric noncoplanar (e, 2e) experiment has been carried out at an incident electron energy of 1.2 keV. Furthermore, theoretical calculations of the electron momentum distributions with vibrational effects being involved have been performed using the harmonic analytical quantum mechanical and Born-Oppenheimer molecular dynamics approaches. In spite of the complex nature of the vibrational structure of this large molecule, both approaches provide overall quantitative insights into the results of the experiment. Comparisons between experiment and theory have shown that ground state nuclear dynamics appreciably affects the momentum profiles of the 7t 2 , {2t 1 +3e}, and {5t 2 +5a 1 } orbitals. It has been demonstrated that changes in the momentum profiles are mainly due to the vibrational motions associated with the CH bonds.