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Photoemission from physisorbed N2: observation of nuclear motion through violation of the sudden approximation

Authors
Journal
Chemical Physics Letters
0009-2614
Publisher
Elsevier
Publication Date
Volume
196
Issue
6
Identifiers
DOI: 10.1016/0009-2614(92)85992-j
Disciplines
  • Physics

Abstract

Abstract N 2 physisorbed on top of a Xe spacer layer on Ag(111) has been studied by angle-resolved UV photoemission in the photon energy range 16.5⩽ hν⩽45 eV. The N 2 1π u valence level exhibits a vibrational fine structure which is composed of two multiplets corresponding to the molecular stretching frequencies in the ionic (ν +) and neutral (ν 0) electronic states. ν 0 gets excited through delocalization of the photohole in the physisorbed layer. The delocalization process occurs during the escape time τ e of the photoelectron (violation of the sudden approximation). By increasing the photon energy, τ e is shortened, which is mirrored in an intensity decrease of the neutral oscillator.

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