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Title: Probing molecular conformations in momentum space: The case of n-pentane
Authors: KNIPPENBERG, Stefan 
HUANG, Yanru 
HAJGATO, Balazs 
FRANCOIS, Jean-Pierre
Deng, J.K.
DELEUZE, Michael 
Issue Date: 2007
Abstract: A comprehensive study, throughout the valence region, of the electronic structure and electron momentum density distributions of the four conformational isomers of n-pentane is presented. Theoretical (e,2e) valence ionization spectra at high electron impact energies (1200 eV+electron binding energy) and at azimuthal angles ranging from 0 degrees to 10 degrees in a noncoplanar symmetric kinematical setup are generated according to the results of large scale one-particle Green's function calculations of Dyson orbitals and related electron binding energies, using the third-order algebraic-diagrammatic construction [ADC(3)] scheme. The results of a focal point analysis (FPA) of relative conformer energies [A. Salam and M. S. Deleuze, J. Chem. Phys. 116, 1296 (2002)] and improved thermodynamical calculations accounting for hindered rotations are also employed in order to quantitatively evaluate the abundance of each conformer in the gas phase at room temperature and reliably predict the outcome of experiments on n-pentane employing high resolution electron momentum spectroscopy. Comparison with available photoelectron measurements confirms the suggestion that, due to entropy effects, the trans-gauche (tg) conformer strongly dominates the conformational mixture characterizing n-pentane at room temperature. Our simulations demonstrate therefore that experimental measurements of (e,2e) valence ionization spectra and electron momentum distributions would very consistently and straightforwardly image the topological changes and energy variations that molecular orbitals undergo due to torsion of the carbon backbone. The strongest fingerprints for the most stable conformer (tt) are found for the electron momentum distributions associated with ionization channels at the top of the inner-valence region, which sensitively image the development of methylenic hyperconjugation in all-staggered n-alkane chains. (c) 2007 American Institute of Physics.
Notes: Hasselt Univ, Dept SBG, B-3590 Diepenbeek, Belgium. Tsing Hua Univ, Dept Phys, Beijing 100084, Peoples R China. Tsing Hua Univ, Key Lab Atom & Mol Nanosci MOE, Beijing 100084, Peoples R China.Deleuze, MS, Hasselt Univ, Dept SBG, Gebouw D, B-3590 Diepenbeek,
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ISSN: 0021-9606
e-ISSN: 1089-7690
DOI: 10.1063/1.2772848
ISI #: 000250787300019
Category: A1
Type: Journal Contribution
Validations: ecoom 2008
Appears in Collections:Research publications

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