硝酸正丙酯和硝酸异丙酯的密度泛函理论研究  

Study on NPN and IPN using density functional theory

作　　者：曾秀琳[1] 陈网桦[2] 刘家骢[2] 阚金玲[2] 

机构地区：[1]淮南师范学院化学系,安徽淮南232001 [2]南京理工大学化工学院,江苏南京210094

出　　处：《计算机与应用化学》2008年第2期201-204,共4页Computers and Applied Chemistry

摘　　要：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。DFT （ B3LYP,B3PW91 and B3P86 ） methods were employed to investigate equilibrium geometry, frontier orbital energy （EHOMO, ELUMO ） and energy gap （ΔE = ELUMO - EHOMO ） as well as bond dissociation energies （BDEs） of n-propyl nitrate （NPN） and isopropyl nitrate （IPN）. The thermal stability of two nitrates and the corresponding radicals were analyzed. The O-NO2 BDEs of NPN and IPN calculated with B3P86 method are close to the experimental values. That the experimental thermolysis of two nitrates is only unimolecular homolytical dissociation of the O-NO2 bonds is corroborated by the finding that the present results of BDE are well coincident with the experimental results of activation energy from literature.

关 键 词：密度泛函理论 硝酸正丙酯 硝酸异丙酯 前线轨道能 键裂解能 

分 类 号：O641.12[理学—物理化学]