Symmetry-adapted perturbation theory energy analysis of alkyl fluorine-aromatic interactions in Torsion balance systems
Persistent URL
Author(s)
Sherman, Mary C.
Ams, Mark R.
Jordan, Kenneth D.
Date Issued
November 23, 2016
Abstract
Symmetry-adapted perturbation theory (SAPT) calculations are carried out to elucidate the intermolecular interactions present between fluorinated and nonfluorinated alkyl chain groups and aromatic π systems in the folded and unfolded
conformers of Wilcox torsion balance systems. The calculations predict the folded conformers to be 2.0−2.3 kcal/mol more stable than the unfolded conformers, with the preference for the folded conformer being greater in the fluorinated alkyl chain case. We also establish that a simple electrostatic analysis, based on atomic charges, is inadequate for understanding the conformational preferences of these systems. In the folded conformers, there are sizable charge penetration contributions that are not recovered by point charge models. Additionally, the SAPT analysis reveals that
exchange−repulsion interactions make a significant contribution to the relative stability of the folded and unfolded conformer.
Journal
The Journal of Physical Chemistry A
Department
Chemistry
Citation
Sherman, M.C., Ams, M.R., and Jordan, K.D. (2016) Symmetry-adapted Perturbation Theory energy analysis of alkyl fluorine-aromatic interactions in Torsion Balance Systems. The Journal of Physical Chemistry A, 120(46), 9292-9298. doi:10.1021/acs.jpca.6b09193
Publisher
American Chemical Society
Version of Article
Published article
DOI
10.1021/acs.jpca.6b09193
ISSN
1089-5639
1520-5215
Rights
"Reprinted (adapted) with permission from (Sherman, M.C., Ams, M.R., and Jordan, K.D. (2016) Symmetry-adapted Perturbation Theory energy analysis of alkyl fluorine-aromatic interactions in Torsion Balance Systems. The Journal of Physical Chemistry A, 120(46), 9292-9298. doi:10.1021/acs.jpca.6b09193). Copyright (2016) American Chemical Society."
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