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2012 , Vol. 70 >Issue 04: 377 - 384

DOI: https://doi.org/10.6023/A1107122

研究论文

OCS, CO2, N2O 与烯、炔烃之间π…π 作用的电子密度拓扑研究

  • 郝静 ,
  • 孟令鹏 ,
  • 孙政 ,
  • 郑世钧 ,
  • 曾艳丽
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  • 河北师范大学化学与材料科学学院 计算量子化学研究所 石家庄 050016

收稿日期: 2011-07-12

  修回日期: 2011-10-17

  网络出版日期: 2011-11-14

基金资助

国家自然科学基金(Nos. 20801017, 20973053, 21073051)、河北省自然科学基金(Nos. B2010000371, B2011205058)、河北省教育厅基金(No. ZD2010126) 资助项目

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Topological Studies on the π…π Interactions between OCS, CO2, N2O and Hydrocarbon

  • Hao Jing ,
  • Meng Lingpeng ,
  • Sun Zheng ,
  • Zheng Shijun ,
  • Zeng Yanli
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  • Institute of Computational Quantum Chemistry, College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang 050016

Received date: 2011-07-12

  Revised date: 2011-10-17

  Online published: 2011-11-14

Supported by

Project supported by the National Natural Science Foundation of China (Nos. 20801017, 20973053, 21073051), the Natural Science Foundation of Hebei Province (Nos. B2010000371, B2011205058), the Education Department Foundation of Hebei Province (No. ZD2010126)

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摘要

采用MP2/aug-cc-pVDZ 方法对氧硫化碳(OCS)、二氧化碳(CO2)、一氧化二氮(N2O)与乙烯(C2H4)、乙炔(C2H2)、 2-丁炔(C4H6)之间形成的平行构型复合物中的分子间相互作用进行了理论研究. 复合物的相互作用能按照B…C2H4 < B…C2H2 < B…C4H6 (B＝OCS, CO2, N2O)的顺序依次增大, 相互作用距离按照B…C2H4>B…C2H2>B…C4H6 (B＝OCS, CO2, N2O)的顺序依次减小. 采用电子密度拓扑分析理论方法, 讨论了复合物中π…π 作用的成键特性. 电子密度拓扑分析表明复合物中形成了弱的分子间相互作用, 且以静电作用为主; π 电子密度分子图与全电子密度分子图中键径方向是一致的, 说明π…π 作用在本文所讨论的体系中起着很重要的作用. NBO 分析表明净电荷迁移从电子给体C2H4, C2H2, C4H6 到电子受体OCS, CO2, N2O, 迁移数按照B…C2H4 < B…C2H2 < B…C4H6 (B＝OCS, CO2, N2O)的顺序依次增大, 与相互作用能的顺序一致.

关键词： 分子间相互作用; 平行构型; 电子密度拓扑分析; π…&pi; 作用; 自然键轨道

本文引用格式

郝静 , 孟令鹏 , 孙政 , 郑世钧 , 曾艳丽 . OCS, CO2, N2O 与烯、炔烃之间π…π 作用的电子密度拓扑研究[J]. 化学学报, 2012 , 70(04) : 377 -384 . DOI: 10.6023/A1107122

Abstract

The parallel-shaped complexes OCS … hydrocarbon, CO2 … hydrocarbon, and N2O … hydrocarbon (hydrocarbon ＝ ethylene, acetylene, dimethylacetylene) were investigated at the MP2/aug-cc-pVDZ level. The interaction energies are along the sequence of B…C2H4 < B…C2H2 < B… C4H6 (B＝OCS, CO2, N2O), and the interaction distances are in sequence of B…C2H4>B…C2H2>B… C4H6 (B＝OCS, CO2, N2O). The π…π interactions were investigated by using the topological analysis of electron density. The nature of interactions of the parallel-shaped complexes belongs to weak electrostatic interactions. The bond paths in the molecular graphs of π electron density and total electron density show the same orientation, indicating that the π…π interactions play an important role in these intermolecular interactions. NBO analyses showed that charge transfers were observed from C2H4, C2H2, C4H6 to OCS, CO2, N2O, and the amount of charge transfer are in sequence of B…C2H4 < B…C2H2 < B…C4H6 (B＝OCS, CO2, N2O), which exactly match the order of the interaction energies.

Key words： intermolecular interaction; the parallel-shaped geometry; topological analysis of electron density; π…&pi; interaction; natural bond orbital (NBO)

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