Explicit solvent effect on cation-pi interactions: a first principle investigation.
Explicit solvent effect on cation-pi interactions: a first principle investigation.
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溶剂对阳离子-π 相互作用的显式影响：第一原理研究。
DOI：
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发表时间：
2009
影响因子：
3.3
通讯作者：
G. N. Sastry
中科院分区：
文献类型：
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作者：
J. S. Rao;H. Zipse;G. N. Sastry
顺序连接的水分子的阳离子-π（Li+-苯，K+-苯，和Mg 2 +-苯）系统表明，阳离子-π相互作用强度在相反的方向上变化，这取决于该网站的阳离子-π系统的溶剂化。金属离子的溶剂化降低了其与π系统的相互作用能，而π系统的溶剂化增加了其与金属离子的相互作用能。与苯结合的阳离子明显增强了芳香族质子参与与水分子氢键结合的能力。金属离子和苯的质心之间的距离固有地随阳离子-π络合物附近的水分子的位置而变化。约化变分空间（RVS）分析表明，π体系的极化能和电荷转移能对总相互作用能有较大贡献.进行分子中的拓扑原子（AIM）分析以评估阳离子-π相互作用的性质。良好的相关性之间的相互作用能和电荷密度在笼临界点的阳离子-π复合物。
Sequential attachment of water molecules to cation-pi (Li+-benzene, K+-benzene, and Mg2+-benzene) systems reveals that the cation-pi interaction strength varies in opposite direction depending on the site of solvation of the cation-pi system. Solvation of the metal ion decreases its interaction energy with the pi system, while the solvation of the pi system increases its interaction energy with the metal ion. The cation binding to benzene clearly enhances the ability of aromatic protons to participate in hydrogen bonding with water molecules. The distance between the metal ion and centroid of the benzene inherently varies with the position of water molecules in the vicinity of cation-pi complex. Reduced variational space (RVS) analysis on bare and solvated cation-pi complexes indicates that the major contributions to the total interaction energy are coming from the polarization and charge transfer energy terms of the pi system. Topological atoms in molecules (AIM) analysis is performed to evaluate the nature of the cation-pi interaction. Good correlations are observed between interaction energies and charge density at the cage critical point of the cation-pi complexes.