采用密度泛函理论B3LYP/6-31G*方法研究了季戊四醇的五个结构相似的硝酸酯基（-ONO2）和叠氮基（-N3）衍生物，包括四叠氮基季戊烷（ TAPE）、三叠氮基季戊醇硝酸酯（ PTAN）、二叠氮基季戊二醇二硝酸酯（ PDADN）、叠氮基季戊三醇三硝酸酯（ PATN）和季戊四醇四硝酸酯（ PETN）。优化了分子几何构型。进行了振动分析。估算了密度、生成热、热力学函数、爆轰性能和比冲。计算了可能的热解引发键的键离解能（ EBD ）和氢转移反应的活化能（ Ea ）。结果表明，与PTAN 、PDADN、 PATN和 PETN比较，TAPE的生成热最大，比冲与PETN相当。 PATN的爆轰性能和稳定性与PETN接近，优于其它衍生物，包括PDADN。含-N3的TAPE的热解由氢转移导致-N3热裂解放出N2引发，其Ea 为130．57 kJ· mol-1。含-ONO2的其它衍生物的热裂解均由O-NO2键断裂开始， EBD为130．91～137．45 kJ· mol-1。这些能量值满足高能化合物的稳定性指标要求。%Five structurally similar-ONO2 and -N3 derivatives of pentaerythritol, including tetraazido pentaerythritol ( TAPE) , pentaerythritol triazido nitrate (PTAN), pentaerythritol diazido dinitrate (PDADN), pentaerythritol azido trinitrate (PATN), and pentaerythritol tetranitrate ( PETN) were studied by the B3LYP/6-31G * method.The molecular geometric configurations were optimized and vibration analyses were performed.Their densities, heats of formation, thermodynamic functions, detonation performances and specific impulses were estimated.The bond dissociation energy ( EBD ) of the possible trigger bond and the acti-vation energy (Ea) of the hydrogen transfer reaction were computed.The results show that in comparison with PTAN, PDADN, PATN and PETN,TAPE has the maximum heat of formation among five derivatives and specific impulse level approaching that of PETN.The detonation performance and stability of PATN are close to those of PETN, and better than that of other derivatives, including PDADN.The pyrolysis of TAPE with-N3 is initiated from the transfer of H to-N3 which leads to the elimination of N2 and has an Ea of 130.57 kJ · mol-1 .The pyrolysis of other derivatives containing -ONO2 is started from the rupture of the O-NO2 bond with an EBD of 130.91~137.45 kJ· mol-1 .These energy values satisfy the stability requirements for the energetic compounds.
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