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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/8259

Title: Study of the photoelectron and electron momentum spectra of cyclopentene using benchmark Dyson orbital theories
Authors: HUANG, Yanru
Ning, Chuan G.
Deng, Jing K.
DELEUZE, Michael
Issue Date: 2008
Citation: PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 10(17). p. 2374-2389
Abstract: A complete study of the valence electronic structure and related electronic excitation properties of cyclopentene in its C-s ground state geometry is presented. Ionization spectra obtained from this compound by means of photoelectron spectroscopy (He I and He II) and electron momentum spectroscopy have been analyzed in details up to electron binding energies of 30 eV using one-particle Green's function (1p-GF) theory along with the outer-valence (OVGF) and the third-order algebraic diagrammatic construction [ADC(3)] schemes. The employed geometries derive from DFT/B3LYP calculations in conjunction with the aug-cc-pVTZ basis set, and closely approach the structures inferred from experiments employing microwave spectroscopy or electron diffraction in the gas phase. The 1p-GF/ADC(3) calculations indicate that the orbital picture of ionization breaks down at electron binding energies larger than similar to 17 eV in the inner-valence region, and that the outer-valence 7a' orbital is also subject to a significant dispersion of the ionization intensity over shake-up states. This study confirms further the rule that OVGF pole strengths smaller than 0.85 foretell a breakdown of the orbital picture of ionization at the ADC(3) level. Spherically averaged (e, 2e) electron momentum distributions at an electron impact energy of 1200 eV that were experimentally inferred from an angular analysis of EMS intensities have been interpreted by comparison with accurate simulations employing ADC(3) Dyson orbitals. Very signi. cant discrepancies were observed with momentum distributions obtained from several outer-valence ionization bands using standard Kohn-Sham orbitals.
Notes: Tsinghua Univ, Dept Phys, Beijing 100084, Peoples R China. Tsinghua Univ, Key Lab Atom & Mol NanoSci MOE, Beijing 100084, Peoples R China. Hasselt Univ, Dept SBG, Res Grp Theoret Chem, B-3590 Diepenbeek, Belgium.Deng, JK, Tsinghua Univ, Dept Phys, Beijing 100084, Peoples R China.djk-dmp@tsinghua.edu.cn michael.deleuze@uhasselt.be
URI: http://hdl.handle.net/1942/8259
DOI: 10.1039/b718588j
ISI #: 000254999000011
ISSN: 1463-9076
Category: A1
Type: Journal Contribution
Validation: ecoom, 2009
Appears in Collections: Research publications

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