[1]李惠萍,于秀丽,高鹏杰,等.基于质子传导机理的四氮唑分子间氢键研究[J].郑州大学学报(工学版),2016,37(03):27-31.[doi:10.13705/j.issn.1671-6833.2016.03.006]
　Li Huiping,Yu Xiuli,Gao Pengjie,et al.Study on the Intermolecular Hydrogen Bonds of Tetrazole Based on Proton Conduction Mechanism[J].Journal of Zhengzhou University (Engineering Science),2016,37(03):27-31.[doi:10.13705/j.issn.1671-6833.2016.03.006]

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基于质子传导机理的四氮唑分子间氢键研究()

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《郑州大学学报(工学版)》[ISSN:1671-6833/CN:41-1339/T]

卷:

37

期数:

2016年03期

页码:

27-31

栏目:

出版日期:

2016-05-10

文章信息/Info

Title:

Study on the Intermolecular Hydrogen Bonds of Tetrazole Based on Proton Conduction Mechanism

作者:

102;  102); font-size: 13px; background-color: rgb(255;  255;  255); font-family: Arial;  Verdana;  sans-serif;">李惠萍;  于秀丽; 高鹏杰; 毛桢东

郑州大学化工与能源学院,河南郑州,450001

Author(s):

Li Huiping;  Yu Xiuli;  Gao Pengjie;  Mao Zhendong

College of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou, Henan, 450001, China

关键词:

四氮唑; N…H—N氢键; 密度泛函理论; 质子传递

Keywords:

tetrazole; N…H—N hydrogen bond; DFT; proton transfer

DOI:

10.13705/j.issn.1671-6833.2016.03.006

文献标志码:

A

摘要:

为了探明四氮唑体系质子传导速率与分子间氢键强度的关系,采用密度泛函理论,在B3 LYP/6-311++G(2d,2p)水平下对四氮唑二聚体N4 CH2-N4CH3进行了几何结构优化和频率分析,重点分析了能量相对较低的8种二聚体的结构、能量、自然键轨道(NBO)和电荷转移量,并采用QST2方法在B3LYP/6-31+ G(d)水平下研究了8种二聚体问质子传递的动态过程,发现了6种过滤态,计算了其传递能垒.结果表明,四氮唑与质子化的四氮唑阳离子通过N…H—N氢键形成分子间相互作用较强的二聚体N4CH2-N4CH3,N…H—N氢键表现出明显的红移特征;N…H—N氢键相互作用稳定化能主要是N原子孤对电子轨道与N—H键反键轨道之间的相互作用;N…H—N氢键强度是影响质子传递能垒大小的主要因素,即直接影响着四氮唑体系中质子的传导速率.

Abstract:

In order to investigate the relationship between proton conduction rate and intermolecular hydrogen bond strength of tetrazole system, the geometric structure optimization and frequency analysis of tetrazole dimer N4 CH2-N4CH3 at the level of B3 LYP/6-311++ G(2d,2p) were carried out by using density flooding theory, focusing on the structure, energy, natural bond orbital (NBO) and The QST2 method was used to study the dynamic processes of proton transfer in the eight dimer interrogations at the B3LYP/6-31+ G(d) level, and six filtered states were found and their transfer energy barriers were calculated. The results showed that tetrazole and protonated tetrazole cations formed the dimer N4CH2-N4CH3 with strong intermolecular interactions through N...H-N hydrogen bonding, and the N...H-N hydrogen bonding exhibited obvious red-shift characteristics; N ...H-N hydrogen bonding interaction stabilization energy is mainly the interaction between the lone pair electron orbital of N atom and the anti-bonding orbital of N-H bond; N...H-N hydrogen bonding strength is the main factor affecting the size of proton transfer energy barrier, i.e. directly affects the proton conduction rate in the tetrazolium system.

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