Potential Energy Curves for Cation-π Interactions: Off-Axis Configurations Are Also Attractive
Potential Energy Curves for Cation-π Interactions: Off-Axis Configurations Are Also Attractive
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DOI：
10.1021/jp906086x
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发表时间：
2009-12-03
影响因子：
2.9
通讯作者：
Sherrill, C. David
中科院分区：
文献类型：
--
作者：
Marshall, Michael S.;Steele, Ryan P.;Sherrill, C. David
利用耦合簇理论，通过微扰三重激发（CCSD(T)）得到了苯-M配合物（M = Li+, Na+， K+和NH4+）的精确势能面。我们的计算表明，离轴阳离子- π相互作用，其中阳离子不是直接在芳香环上，可能是有利的，并可能影响分子识别。即使是垂直的，侧向相互作用在气相中也保留了18-32%的面相互作用能，使它们的键强度与气相中的氢键相当。利用极化连续体模型探讨了每种配合物的溶剂效应。
Accurate potential energy surfaces for benzene-M complexes (M = Li+, Na+, K+, and NH4+) are obtained using coupled-cluster theory through perturbative triple excitations, CCSD(T). Our computations show that off-axis cation-pi interactions, where the cation is not directly above the aromatic ring, can be favorable and may influence molecular recognition. Even perpendicular, side-on interactions retain 18-32% of their pi-face interaction energy in the gas phase, making their bond strengths comparable to hydrogen bonds in the gas phase. Solvent effects have been explored for each complex using the polarizable continuum model.