AI Article Synopsis
- The study uses symmetry-adapted perturbation theory (SAPT) to analyze how fluorinated and nonfluorinated alkyl chains interact with aromatic structures in different conformations of Wilcox torsion balances.
- The findings indicate that folded conformers are 2.0-2.3 kcal/mol more stable than their unfolded counterparts, with greater stability seen in the fluorinated versions.
- The research highlights that relying solely on electrostatic models based on atomic charges is insufficient, as it overlooks significant charge penetration effects and the important role of exchange-repulsion interactions in determining conformational stability.
Article 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.
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| http://dx.doi.org/10.1021/acs.jpca.6b09193 | DOI Listing |
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