【摘要】 在B3LYP/6-31G(d,p)、MP4(SDTQ)/6-31G(d,p)、G3MP2B3等多种水平下计算了FOX-7的两种有分歧的起始热分解方式反应物、中间体和过渡态的能量,并以高水平的G3MP2B3方法得到的能量为准,计算了硝基断裂反应和异构化反应在温度范围2503300K下的速率常数。结果表明,在高温下FOX-7的主要起始热分解方式是C—NO2键断裂,与从头算分子动力学模拟结果相一致。探讨了FOX-7分解生成的NO2对FOX-7分解的影响,计算结果表明,有NO2存在时,分解能垒会降低,FOX-7的分解会加速。更多还原

【Abstract】 B3LYP/6-31G（d, p）, MP4（SDTQ）/6-31G（d, p） and G3MP2B3 methods were used to calculate the energy of the decomposition species of FOX-7. Based on the energy obtained by G3MP2B3 method, the rate constants of C—NO₂ cleavage and nitro-to-nitrite rearrangement were calculated in the temperature range of 250-3300 K. It is found that C—NO₂ cleavage is the dominant initial thermal decomposition step at high temperature which is consistent with the conclusion based on ab initio molecular dynamics simulation. The effects of NO₂ on the FOX-7 decomposition were investigated. Results show that the decomposition energy barrier becomes lower when NO₂ reacts with FOX-7.更多还原