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Theoretical Study on Intermolecular Interactions of Ethyl Azide Dimers
Xia Qiying, Xiao Heming*, Ju Xuehai, Gong Xuedong
Department of Chemistry,Nanjing University of Science and Technology,Nanjing 210094
Abstract:
Energetic materials are aggregative and mixed systems. The intermolecular interactions play significantroles in the physical,chemical and explosive property. The study on intermolecular interactions of energetic materials has attracted wide attention. The organic azides are an important category of energetic materials and widely used in many fields. Ethyl azide is the simple model having the explosive property for the organic azides energetic compound. Ethyl azide monomer(Ⅰ)and all its possible stable clusters(Ⅱ,Ⅲ and Ⅳ)are fully optimized by ab initio method at the HF/6-311++G** level. Vibrational frequencies calculated to ascertain each structure are characterized to be the stable structure(no imaginary frequencies). The proportions of correlated interaction energies to their total interaction energies ΔE(MP2)are 65.14%,63.76% and 65.62% for Ⅱ,Ⅲ and Ⅳ respectively. In addition,the basis set superposition error(BSSE)correction energies are 7.82,7.61 and 4.40 kJ/mol for Ⅱ,Ⅲ and Ⅳ respectively. The zero point energy (ZPE) corrections for the interaction energies are much less than those of MP2 electron correlation and BSSE correction energies. After MP2 electron correlation correction,BSSE and ZPE correction,the greatest corrected intermolecular interaction of the dimers is -10.45 kJ/mol. The charge redistribution mainly occurs on the adjacent N?H atoms between submolecules. The charge transfer between two subsystems is very small. Natural bond orbital(NBO)analysis is performed to reveal the origin of the interaction. Based on the statistical thermodynamic method,the standard thermodynamic functions,heat capacities(C0p),entropies(S0m)and enthalpies(H0m)and the changes of thermodynamic properties from the monomer to dimer with the temperatures ranging from 200. 00 K to 800. 00 K have been obtained.
Key words:  Ethyl azide dimer,Intermolecular interaction,ab initio,Natural bond orbital,Thermodynamic properties
FundProject:
叠氮乙烷二聚体分子间相互作用的理论研究
夏其英, 肖鹤鸣*, 居学海, 贡雪东
南京理工大学化学系,南京 210094
摘要:
用ab initio HF/6-311++G**计算求得叠氮乙烷二聚体势能面上三种优化构型和电子结构. 经MP2电子相关校正和基组叠加误差(BSSE)以及零点能(ZPE)校正,求得分子间最大相互作用能为-10.45 kJ/mol. 二子体系间的电荷转移很少. 由自然键轨道(NBO)分析揭示了相互作用的本质. 基于统计热力学求得温度为200. 00~800. 00 K从单体形成二聚体的热力学性质变化.
关键词:  叠氮乙烷二聚体  分子间相互作用  从头计算  自然键轨道(NBO)  热力学性质
DOI:10.1088/1674-0068/17/1/45-50
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