Unraveling weak interactions in aniline-pyrrole dimer clusters

作     者：Chengqian Yuan Pan An Jing Chen Zhixun Luo Jiannian Yao 

作者机构：Beijing National Laboratory for Molecular SciencesInstitute of ChemistryChinese Academy of SciencesBeijing 100190China Graduate University of Chinese Academy of SciencesBeijing 100049China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2016年第59卷第10期

页      面：1270-1276页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：supported by the National Project“Development of Advanced Scientific Instruments Based on Deep Ultraviolet Laser Source”(Y31M0112C1) the National Basic Research Program of China(2011CB808402) Z.Luo acknowledges the Young Professionals Programme in Institute of Chemistry,Chinese Academy of Sciences(ICCAS-Y3297B1261) 

主　　题：weak intermolecular interactions aniline pyrrole dimer cluster hydrogen bonding nature bond orbital energy decomposition 

摘      要：Weak intermolecular interactions in aniline-pyrrole dimer clusters have been studied by the dispersion-corrected density functional theory(DFT) calculations. Two distinct types of hydrogen bonds are demonstrated with optimized geometric structures and largest interaction energy moduli. Comprehensive spectroscopic analysis is also addressed revealing the orientation-dependent interactions by noting the altered red-shifts of the infrared and Raman activities. Then we employ natural bond orbital(NBO)analysis and atom in molecules(AIM) theory to have determined the origin and relative energetic contributions of the weak interactions in these systems. NBO and AIM calculations confirm the V-shaped dimer cluster is dominated by N.H···N and C.H···π hydrogen bonds, while the J-aggregated isomer is stabilized by N.H···π, n→π* and weak π···π* stacking *** noncovalent interactions are also demonstrated via energy decomposition analysis associated with electrostatic and dispersion contributions.