4-氨基-3,5-二硝基吡唑二聚体分子间相互作用的理论研究（英文）

Theoretical study on intermolecular interactions of 4-amino-3,5-dinitropyrazole dimers

在密度泛函(DFT)B3LYP/6-311++G^(**)水平下,求得4-氨基-3,5-二硝基吡唑(LLM-116)二聚体势能面上的4种全优化几何构型.经基组叠加误差(BSSE)和零点能(ZPE)校正,求得分子间最大相互作用能为-29.56 k J·mol^(-1).研究表明,其相互作用是放热过程,并随着温度的升高,相互作用减弱;自然键轨道(NBO)分析揭示了相互作用的本质;对优化构型进行振动分析,得其红外光谱,并基于统计热力学求得200.0-800.0 K温度范围从单分子形成二聚体的热力学性质变化.

Density functional theory （DFT） method with 6 - 311 ＋＋ G^ ＊ ＊ basis set was applied to study intermo- lecular interactions of 4 - amino - 3,5 - dinitropyrazole （ LLM - 116 ） dimers. Four optimized stable LLM - 116 dimers were found on the potential energy surface. The intermolecular interaction energy was calculated with basis set superposition error （BSSE） correction and zero point energy （ZPE） correction. The greatest corrected intermolecular interaction energy of the dimer is - 29.56 kJ · mol^- 1. The intermolecular interaction is an exothermic process accompanied by a decrease in the probability of dimers formation, and the interactions become weak as temperature increase. Natural bond orbital （NBO） analysis was performed to reveal the origin of interaction. The IR spectra were obtained and assigned by vibrational analysis. Based on vibrational analysis, the changes of thermodynamic properties from monomer to dimer with temperature ranging from 200. 0 to 800. 0 K were obtained using statistical thermodynamic method.