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用密度泛函理论(DFT)中的B3LYP、B3PW91、B3P86方法研究硝酸正丙酯(n-propyl nitrate,NPN)和硝酸异丙醣(isopro- pyl nitrate,IPN)的平衡分子构型、前线轨道能(E_(HOMO)、E_(LUMO))、能差(△E=E_(LUMO)-E_(HOMO))和O-NO_2键的裂解能(BDE)。分析了两种硝酸酯分子和对应自由基的热稳定性。NPN和IPN中的O-NO_2键的裂解能用B3P86方法计算出最接近实验值。由O- NO_2键的裂解能符合文献中对应物质的表观活化能,推知两种物质的热分解反应只是单分子O-NO_2键的均裂反应。
The equilibrium molecular configurations of n-propyl nitrate (NPN) and isopro-pyl nitrate (IPN) were studied by B3LYP, B3PW91 and B3P86 methods in density functional theory (DFT) (E_ (HOMO) and E_ (LUMO)), energy difference (△ E = E_LUMO-HOMO) and O-NO_2 bond energy (BDE). The thermal stability of the two nitrate esters and the corresponding free radicals was analyzed. The cleavage of O-NO 2 bonds in NPN and IPN can be calculated using the B3P86 method closest to the experimental value. The cleavage of O-NO 2 bonds can be in accordance with the apparent activation energy of the corresponding materials in the literature, inferring that the thermal decomposition reaction of the two materials is only the cleavage reaction of the single-molecule O-NO 2 bond.