物理化学学报 >> 2007, Vol. 23 >> Issue (02): 192-197.doi: 10.1016/S1872-1508(07)60015-1

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炸药敏化剂的分子结构、电子结构和生成热的理论研究

曾秀琳;陈网桦;刘家骢   

  1. 南京理工大学化工学院, 南京 210094
  • 收稿日期:2006-06-21 修回日期:2006-09-14 发布日期:2007-02-01
  • 通讯作者: 曾秀琳 E-mail:zengxiulin1992@163.com

Theoretical Studies on the Molecular Structure, Electronic Structure and Heats of Formation of Explosive Sensitizers

ZENG Xiu-Lin;CHEN Wang-Hua;LIU Jia-Cong   

  1. School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. China
  • Received:2006-06-21 Revised:2006-09-14 Published:2007-02-01
  • Contact: ZENG Xiu-Lin E-mail:zengxiulin1992@163.com

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摘要： 在HF/6-31G*和B3LYP/6-31G*基组水平上, 对硝酸乙酯(EN)、硝酸正丙酯(NPN)、硝酸异丙酯(IPN)、硝酸异辛酯(EHN)和四甘醇二硝酸酯(TEGDN)五种炸药敏化剂进行理论计算, 研究了标题物的分子结构、电子结构和能量等方面的性质. 基于Mulliken布居和键长分析, 五种硝酸酯分子的热分解始于O2—N3键的断裂, 且由Mulliken电荷分布推知分子热解产生NO2气体. 在分析前线轨道能(EHOMO, ELUMO)和能量差(ΔE)的基础上对五种硝酸酯的相对热稳定性大小进行了评估. 由等键反应获得的EN、IPN、NPN、EHN和TEGDN的标准生成热分别是-155.972、-190.896、-175.279、-272.376和-790.733 kJ·mol-1.

关键词: 炸药敏化剂, Mulliken布居, 前线轨道能, 生成热, 等键反应

Abstract: Quantum chemical calculations at the HF/6-31G* and B3LYP/6-31G* levels have been carried out on five explosive sensitizers: ethyl nitrate (EN), n-propyl nitrate (NPN), isopropyl nitrate (IPN), 2-ethylhexyl nitrate (EHN), and tetraethylene glycol dinitrate (TEGDN). Theoretical studies have yielded a wealth of quantum chemical information on the molecular geometries, electronic structures, and energies of the title compounds. On the basis of the Mulliken populations and bond lengths, the O2—N3 fission is acceptable. Charge distribution analysis indicated that the five nitrates produced NO2 gas during the dissociation of the O2—N3 weak bond. The relative thermal stability ordering of the five nitrates was estimated on the basis of the frontier orbital energy (EHOMO, ELUMO) and the energy gap (ΔE). The heats of formation (HOFs) of the five sensitizers, EN, IPN, NPN, EHN, and TEGDN, were calculated from the isodesmic reactions and were -155.972, -190.896, -175.279, -272.376, and -790.733 kJ·mol-1, respectively.

Key words: Explosive sensitizers, Mulliken population, Frontier orbital energy, Heat of formation (HOF), Isodesmic reaction