文献类型：期刊文献

英文题名：Carbocation-π interaction with Car-Parrinello molecular dynamics: Ab initio molecular dynamics investigation of complex of methyl cation with benzene

作者：Zheng, Fei[1]; Sa, Rongjian[1]; Cheng, Jiagao[2]; Jiang, Hualiang[1]; Shen, Jianhua[1]

机构：[1] Drug Discovery and Design Center, State Key Laboratory of New Drug Research, Shanghai Institute of Materia Medica, 555 Zu Chong Zhi Road, Shanghai 201203, China; [2] School of Pharmacy, East China University of Science and Technology, Shanghai, 200237, China

年份：2007

卷号：435

期号：1-3

起止页码：24

外文期刊名：Chemical Physics Letters

收录：EI(收录号：20070510397832)

语种：英文

外文关键词：Benzene - Charge transfer - Computer simulation - Mathematical models - Optimization - Positive ions

摘要：Cation-π interaction plays an important role as a general noncovalent binding force in a wide range of systems. To examine the more stable state of carbocation-π complex, we have carried out Car-Parrinello molecular dynamics (CPMD) simulations of six models. These results are proved to be reliable from the comparison with those of investigations by ab initio calculations. Charge transfer and molecular orbital interaction are discussed to depict the interaction modes of different models. From our CPMD studies without restraints, the methyl group moves toward the side of the benzene forming a stable σ-complex. However, if the methyl group is maintained above benzene, the inter-conversions among different models of C6 H6 {single bond} CH3+ complex, which are determined from ab initio optimization, are observed; and distances between the carbon of methyl group and the center of benzene range from 2.67 ? to 3.61 ?. Our results provide a dynamic process concerning the motion of methyl group above the benzene ring. ? 2006 Elsevier B.V. All rights reserved.