Substituent effects in π-π interactions:: Sandwich and T-shaped configurations
Substituent effects in π-π interactions:: Sandwich and T-shaped configurations
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DOI：
10.1021/ja049434a
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发表时间：
2004-06-23
影响因子：
15
通讯作者：
Sherrill, CD
中科院分区：
文献类型：
--
作者：
Sinnokrot, MO;Sherrill, CD
用偶联簇理论研究了苯二聚体、苯-苯酚、苯-甲苯、苯-氟苯和苯-苯腈的夹心和t形构型，以阐明取代基如何调节pi-pi相互作用。所有取代的三明治二聚体结合比苯二聚体更强，而t形构型结合或多或少有利取决于取代基。对称自适应微扰理论（SAPT）表明，静电、色散、感应和交换排斥对总结合能的贡献都很重要，除感应外，其他因素在确定相对能量方面都很重要。仅仅基于静电的pi-pi相互作用模型，如亨特-桑德斯规则，似乎无法解释二聚体的能量排序；考虑。
Sandwich and T-shaped configurations of benzene dimer, benzene-phenol, benzene-toluene, benzene-fluorobenzene, and benzene-benzonitrile are studied by coupled-cluster theory to elucidate how substituents tune pi-pi interactions. All substituted sandwich dimers bind more strongly than benzene dimer, whereas the T-shaped configurations bind more or less favorably depending on the substituent. Symmetry-adapted perturbation theory (SAPT) indicates that electrostatic, dispersion, induction, and exchange-repulsion contributions are all significant to the overall binding energies, and all but induction are important in determining relative energies. Models of pi-pi interactions based solely on electrostatics, such as the Hunter-Sanders rules, do not seem capable of explaining the energetic ordering of the dimers; considered.