Please use this identifier to cite or link to this item:
http://hdl.handle.net/1942/894
Title: | Probing Molecular Conformations with Electron Momentum Spectroscopy: The Case of n-Butane | Authors: | DELEUZE, Michael Pang, W.N. Shang, R.C. SALAM, Akbar |
Issue Date: | 2001 | Publisher: | ACS | Source: | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 123(17). p. 4049-4061 | Abstract: | High-resolution (e,2e) measurements of the valence electronic structure and momentum-space electron density distributions of n-butane have been exhaustively reanalyzed in order to cope with the presence of two stable structures in the gas phase, namely the all-staggered and gauche conformers. The measurements are compared to a series of Boltzmann-weighted simulations based on the momentum-space form of Kohn-Sham (B3LYP) orbital densities, and to ionization spectra obtained from high-level [ADC(3)] one-particle Green's Function calculations. Indubitable improvements in the quality of the simulated (e,2e) ionization spectra and electron momentum profiles are seen when the contributions of the gauche form of n-butane are included. Both the one-electron binding energies and momentum distributions consistently image the distortions and topological changes that molecular orbitals undergo due to torsion of the carbon backbone, and thereby exhibit variations which can be traced experimentally. With regard to the intimate relation of (e,2e) cross sections with orbital densities, electron momentum spectroscopy can therefore be viewed as a very powerful, but up to now largely unexploited, conformational probe. The study also emphasizes the influence of thermal agitation in photoionization experiments of all kind. | Keywords: | ANGLE-RESOLVED PHOTOEMISSION; TORSIONAL POTENTIAL FUNCTION; ENERGY-BAND DISPERSION; STATIC SELF-ENERGY; HARTREE-FOCK LIMIT; SYNCHROTRON-RADIATION; EMS MEASUREMENTS; GREENS-FUNCTION; CONFIGURATION-INTERACTION; VIBRATIONAL-SPECTRA | Document URI: | http://hdl.handle.net/1942/894 | ISSN: | 0002-7863 | e-ISSN: | 1520-5126 | DOI: | 10.1021/ja0039886 | ISI #: | 000168442700023 | Category: | A1 | Type: | Journal Contribution | Validations: | ecoom 2002 |
Appears in Collections: | Research publications |
Show full item record
SCOPUSTM
Citations
62
checked on Sep 3, 2020
WEB OF SCIENCETM
Citations
66
checked on Apr 14, 2024
Page view(s)
34
checked on Jun 28, 2023
Google ScholarTM
Check
Altmetric
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.