Please use this identifier to cite or link to this item:
http://hdl.handle.net/1942/2166
Title: | The band 12 issue in the electron momentum spectra of norbornane: A comparison with additional Green's Function calculations and ultraviolet photoemission measurements | Authors: | KNIPPENBERG, Stefan DELEUZE, Michael CLEIJ, Thomas FRANCOIS, Jean-Pierre Cederbaum, LS Eland, JHD |
Issue Date: | 2005 | Publisher: | AMER CHEMICAL SOC | Source: | JOURNAL OF PHYSICAL CHEMISTRY A, 109(19). p. 4267-4273 | Abstract: | In continuation of a recent study of the electronic structure of norbornane [J. Chem. Phys., 2004, 121, 10525] by means of electron momentum spectroscopy (EMS), we present Green's Function calculations of the ionization spectrum of this compound at the ADC(3) level using basis sets of varying quality, along with accurate evaluations at the CCSD(T) level of the vertical (26.5 eV) and adiabatic (22.1 eV) double ionization thresholds under C-2v symmetry. The obtained results are compared with newly recorded ultraviolet photoemission spectra (UPS), up to binding energies of 40 eV. The theoretical predictions are entirely consistent with experiment and indicate that, in a vertical depiction of ionization, shake-up states at binding energies larger than ∼ 26.5 eV tend to decay via emission of a second electron in the continuum. A band of s-type symmetry that has been previously seen at ∼ 25 eV in the electron impact ionization spectra of norbornane is entirely missing in the UPS measurements and theoretical ADC(3) spectra. With regard to these results and to the time scales characterizing electron-electron interactions in EMS (10(-17) s) as compared with that (10(-13) s) of photon-electron interactions in UPS, and considering the p-type symmetry of the electron momentum distributions for the nearest 1b(1) and 1b(2) orbitals, this additional band can certainly not be due to adiabatic double ionization processes starting from the ground electronic state of norbornane, or to exceptionally strong vibronic coupling interactions between cationic states derived from ionization of the latter orbitals. It is therefore tentatively ascribed to autoionization processes via electronically excited and possibly dissociating states. | Notes: | Limburgs Univ Ctr, Dept SBG, B-3590 Diepenbeek, Belgium. Univ Heidelberg, Inst Phys Chem, D-69120 Heidelberg, Germany.Deleuze, MS, Limburgs Univ Ctr, Dept SBG, Univ Campus, B-3590 Diepenbeek, Belgium.deleuze@luc.ac.be | Document URI: | http://hdl.handle.net/1942/2166 | ISSN: | 1089-5639 | e-ISSN: | 1520-5215 | DOI: | 10.1021/jp044130w | ISI #: | 000229134300009 | Category: | A1 | Type: | Journal Contribution | Validations: | ecoom 2006 |
Appears in Collections: | Research publications |
Show full item record
SCOPUSTM
Citations
18
checked on Sep 3, 2020
WEB OF SCIENCETM
Citations
19
checked on Oct 12, 2024
Page view(s)
62
checked on Sep 7, 2022
Google ScholarTM
Check
Altmetric
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.