Tunable Fictitious Substituent Effects on the 蟺鈥撓€ Interactions of Substituted Sandwich Benzene Dimers

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• 作者：Amee M. Garcia ; John J. Determan ; Benjamin G. Janesko
• 刊名：Journal of Physical Chemistry A
• 出版年：2014
• 出版时间：May 8, 2014
• 年：2014
• 卷：118
• 期：18
• 页码：3344-3350
• 全文大小：329K
• 年卷期：v.118,no.18(May 8, 2014)
• ISSN：1520-5215

文摘

Substituent effects on the 蟺鈥撓€ interactions of aromatic rings are a topic of much recent debate. Real substituents give a complicated combination of inductive, resonant, dispersion, and other effects. To help partition these effects, we present calculations on fictitious 鈥減ure鈥?蟽 donor/acceptor substituents, hydrogen atoms with nuclear charges other than 1. 鈥淧ure鈥?蟽 donors with nuclear charge <1 weaken 蟺鈥撓€ stacking in the sandwich benzene dimer. This result is consistent with the electrostatic model of Hunter and Sanders, and different from real substituents. Calculated inductive effects are largely additive and transferable, consistent with a local direct interaction model. A second series of fictitious substituents, neutral hydrogen atoms with an artificially broadened nuclear charge distribution, give similar trends though with reduced additivity. These results provide an alternative perspective on substituent effects in noncovalent interactions.