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Title: Investigation into the valence electronic structure of norbornene using electron momentum spectroscopy, green's function, and density functional theories
Authors: KNIPPENBERG, Stefan 
Nixon, KL
Mackenzie-Ross, H
Brunger, MJ
Wang, F
DELEUZE, Michael 
FRANCOIS, Jean-Pierre
Winkler, DA
Issue Date: 2005
Source: JOURNAL OF PHYSICAL CHEMISTRY A, 109(41). p. 9324-9340
Abstract: Results of a study of the valence electronic structure of norbornene (C7H10), up to binding energies of 30 eV, are reported. Experimental electron momentum spectroscopy (EMS) and theoretical Green's function and density functional theory approaches were utilized in this investigation. A stringent comparison between the electron momentum spectroscopy and theoretical orbital momentum distributions found that, among the tested models, the combination of the Becke-Perdew functional and a polarized valence basis set of triple-zeta quality provides the best representation of the electron momentum distributions for all 19 valence orbitals of norbornene. This experimentally validated model was then used to extract other molecular properties of norbornene (geometry, infrared spectrum). When these calculated properties are compared to corresponding results from independent measurements, reasonable agreement is typically found. Due to the improved energy resolution, EMS is now at a stage to very finely image the effective topology of molecular orbitals at varying distances from the molecular center, and the way the individual atomic components interact with each other, often in excellent agreement with theory. This will be demonstrated here. Green's Function calculations employing the third-order algebraic diagrammatic construction scheme indicate that the orbital picture of ionization breaks down at binding energies larger than about 22 eV. Despite this complication, they enable insights within 0.2 eV accuracy into the available ultraviolet emission and newly presented (e,2e) ionization spectra. Finally, limitations inherent to calculations of momentum distributions based on Kohn-Sham orbitals and employing the vertical depiction of ionization processes are emphasized, in a formal discussion of EMS cross sections employing Dyson orbitals.
Notes: Hasselt Univ, Dept SBG, Theoret Chem Grp, B-3590 Diepenbeek, Belgium. Flinders Univ S Australia, Sch Chem Phys & Earth Sci, Adelaide, SA 5001, Australia. Swinburne Univ Technol, Ctr Mol Simulat, Hawthorn, Vic 3122, Australia. CSIRO Mol Sci, Clayton, Vic 3169, Australia. Monash Univ, Sch Chem, Melbourne, Vic 3168, Australia.Brunger, MJ, Hasselt Univ, Dept SBG, Theoret Chem Grp, Gebouw D, B-3590 Diepenbeek,
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ISSN: 1089-5639
e-ISSN: 1520-5215
DOI: 10.1021%2Fjp058158z
ISI #: 000232612000018
Category: A1
Type: Journal Contribution
Validations: ecoom 2006
Appears in Collections:Research publications

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