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Conformational Effects on Circular Dichroism in the Photoelectron Angular Distribution
Author(s) -
Di Tommaso Devis,
Stener Mauro,
Fronzoni Giovanna,
Decleva Piero
Publication year - 2006
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200500602
Subject(s) - dichroic glass , conformational isomerism , valence (chemistry) , chemistry , asymmetry , circular dichroism , dichroism , molecule , density functional theory , vibrational circular dichroism , crystallography , computational chemistry , molecular physics , materials science , physics , optics , nanotechnology , organic chemistry , quantum mechanics
10.1002/cphc.200500602.abs The B‐spline density‐functional method has been applied to the conformers of the (1 R , 2 R )‐1,2‐dibromo‐1,2‐dichloro‐1,2‐difluoroethane molecule. The cross section, asymmetry, and dichroic parameters relative to core and valence orbitals, which do not change their nature along the conformational curve, have been systematically studied. While the cross section and the asymmetry parameter are weakly affected, the dichroic parameter appears to be rather sensitive to the particular conformer of the molecule, suggesting that this dynamical property could be a useful tool for conformational analysis. The computational method has also been applied to methyl rotation in methyloxirane. Unexpected and dramatic sensitivity of the dichroic‐parameter profile to the methyl rotation, both in the core and valence states, has been found. Boltzmann averaging over the conformers reproduces quite closely the profiles previously obtained for the minimum‐energy conformation, which is in good agreement with the experimental results.