摘要
运用从头计算方法 ,在HF/6 - 31 1 + +G 水平上 ,求得叠氮乙烯二聚体势能面上 3种稳定的分子几何和电子结构。经二级微扰MP2电子相关校正和基组叠加误差以及零点能校正 ,求得分子间最大相互作用能为 - 8.6 6kJ/mol。由自然键轨道分析揭示了相互作用的本质 ,发现二子体系间的电荷转移较少。基于统计热力学求得 2 73.1 5～ 70 0 .0 0K温度范围从单体形成二聚体的热力学性质变化。为有机叠氮高能体系中分子间相互作用的理论研究提供了首例和基础数据。
Three optimized stable azidoethene dimers found on the potential energy surface and their electronic structures have been obtained by using ab initio method at the HF/6-311++G** level. The intermolecular interaction energy is calculated with MP2 electron correlation correction, basis set superposition error correction and zero point energy correction. The greatest corrected intermolecular interaction of the dimers is -8.66 kJ/mol. Natural bond orbital analysis is performed to reveal the origin of the interaction. Charge transfer between two subsystems is small. Based on the statistical thermodynamic method, the changes of thermodynamic properties from the monomer to dimer with the temperature ranging from 273.15 to 700.00 K have been obtained. These provide a pioneer model and basic data for theoretical study on intermolecular interaction of organic azides energetic compound.
出处
《南京理工大学学报》
EI
CAS
CSCD
北大核心
2003年第5期502-508,共7页
Journal of Nanjing University of Science and Technology
基金
国家自然科学基金 (2 0 1730 2 8)
国防科工委基础研究项目
