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

64
checked on May 13, 2022

Page view(s)

14
checked on May 17, 2022

Google ScholarTM

Check

Altmetric


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.