二聚体C2H4-nFn···LiH (n=0, 1, 2)中π锂键的性质和弱方向性

doi:10.3866/PKU.WHXB201208291

物理化学学报 >> 2012, Vol. 28 >> Issue (12): 2817-2823.doi: 10.3866/PKU.WHXB201208291

二聚体C₂H_4-nF_n···LiH (n=0, 1, 2)中π锂键的性质和弱方向性

王树建, 李莹, 吴迪

吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春 130023

收稿日期:2012-07-05 修回日期:2012-08-27 发布日期:2012-11-14
通讯作者: 吴迪 E-mail:wud@mail.jlu.edu.cn
基金资助:
国家自然科学基金(21173095)资助项目

Properties and Weak Directionality of the π-Lithium Bond in C₂H_4-nF_n···LiH (n =0, 1, 2) Dimers

WANG Shu-Jian, LI Ying, WU Di

State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, P. R. China

Received:2012-07-05 Revised:2012-08-27 Published:2012-11-14
Supported by:
The project was supported by the National Natural Science Foundation of China (21173095).

摘要/Abstract

摘要：

采用二级微扰理论(MP2)量子化学研究方法, 对C₂H_4-nF_n···LiH (n=0, 1, 2)二聚体的结构和π锂键性质进行了分析. 结果表明氟原子的取代改变了乙烯分子的π电子云形状, 从而使二聚体体系中的π锂键发生偏移、伸长和弯曲. 通过与类似的π氢键体系C₂H_4-nF_n···HF (n=0, 1, 2)比较, 发现π锂键在二级弱相互作用的影响下, 发生了明显的弯曲, 表现出弱的方向性. 在CCSD(T)/6-311++G(3df, 3pd)理论水平下, 二聚体的相互作用能强弱顺序为: 33.85 kJ·mol^-1 (C₂H₄-LiH)>27.32 kJ·mol^-1 (C₂H₃F-LiH)>21.34 kJ·mol^-1 (cis-C₂H₂F₂-LiH)>20.25 kJ·mol^-1 (g-C₂H₂F₂-LiH), 说明氟取代削减了乙烯分子与LiH之间的相互作用.

关键词: π锂键, π氢键, 弱相互作用, 二级微扰理论, 取代效应

Abstract:

Using the second-order Møller-Plesset perturbation method, the structures and π-lithium bonding properties of C₂H_4-nF_n···LiH (n=0, 1, 2) dimers were analyzed. The results showed that F substitution led to π electron cloud deformation in the ethylene molecule, and subsequent changes (deviation, elongation, and bend) in the π-lithium bonds in C₂H_4-nF_n···LiH. In contrast to the π-hydrogen bonds in the C₂H_4-nF_n···LiH (n=0, 1, 2) systems, the π-lithium bonds in the C₂H_4-nF_n···LiH dimers were obviously bent because of secondary hydrogen bond interactions, and they exhibited weak directivity. For the four C₂H_4-nF_n···LiH dimers, the strength of the interaction was 33.85 kJ·mol^-1 (C₂H₄-LiH)>27.32 kJ·mol^-1 (C₂H₃F-LiH)>21.34 kJ·mol^-1 (cis-C₂H₂F₂-LiH)>20.25 kJ·mol^-1 (g-C₂H₂F₂-LiH) at the CCSD(T)/6-311++G(3df, 3pd) level. This indicates that the F substituent effect decreases the strength of the interaction between ethylene and LiH molecules.

Key words: π-Lithium bond, π-Hydrogen bond, Weak interaction, Second-order Mø, ller-Plesset perturbation theory, Substituent effect

王树建, 李莹, 吴迪. 二聚体C₂H_4-nF_n···LiH (n=0, 1, 2)中π锂键的性质和弱方向性[J]. 物理化学学报, 2012, 28(12), 2817-2823. doi: 10.3866/PKU.WHXB201208291

WANG Shu-Jian, LI Ying, WU Di. Properties and Weak Directionality of the π-Lithium Bond in C₂H_4-nF_n···LiH (n =0, 1, 2) Dimers[J]. Acta Phys. -Chim. Sin. 2012, 28(12), 2817-2823. doi: 10.3866/PKU.WHXB201208291

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201208291

https://www.whxb.pku.edu.cn/CN/Y2012/V28/I12/2817

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二聚体C₂H_4-nF_n···LiH (n=0, 1, 2)中π锂键的性质和弱方向性

Properties and Weak Directionality of the π-Lithium Bond in C₂H_4-nF_n···LiH (n =0, 1, 2) Dimers

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