硝酸羟胺离子间相互作用的密度泛函理论研究

摘要

To study the interactions of hydroxylamine nitrate ion,the geometry of hydroxylamine nitrate ion pair was optimized using the B3LYP/6-311 + + G (d,p)method.The atomic net charge was calculated by natural population analysis and the theoretical research of H atom transfer in the process of ion pair system formation was carried out.The interaction energy of ion pair was calculated by basis set superposition error (BSSE)and zero point energy correction (ZPEC).The thermodynamic properties of hydroxylamine nitrate ion pair in the temperature range of 200 to 800 K were calculated using the statistical thermodynamic method.The results show that the reaction barrier of H atom transfer in the process of ion pair formation is 46.605kJ/mol.The ion pair manifests as the nature of interactions between HNO3 and NH2 OH.The interaction energy of the configuration II is greatest,as-48.145 kJ/mol,and the stability decreases in the order of configuration II>configuration III>configuration IV. Configurations II and III can be spontaneously formed at the room temperature,while configuration IV can only be formed spontaneously at lower temperature below 200 K.%为研究硝酸羟胺离子间的相互作用，采用 DFT-B3LYP／6-311＋＋G（d，p）方法，对硝酸羟胺离子对的几何构型进行优化；通过自然集居分析计算了各原子的净电荷，并针对离子对体系形成过程中 H 原子的转移进行了理论研究；通过基组叠加误差（BSSE）和零点能校正（ZPEC）计算了离子对的相互作用能；用统计热力学方法对硝酸羟胺离子对在200～800 K 的热力学性质进行了计算。结果表明，离子对形成过程中 H 原子转移的反应势垒为46．605 kJ／mol，离子对表现为 HNO3和 NH2 OH 之间相互作用的性质；构型 II 的相互作用能最大，为－48．145 kJ／mol，稳定性排列顺序为构型 II＞构型 III＞构型 IV；另外，构型 II 和构型 III 在常温下即可自发形成，构型 IV 只能在200 K 以下的低温才能自发形成。