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该文用ab initio和MNDO方法计算研究了硝酸甲酯(MN)及其自由基正离子(MN~+)的平衡几何构型、电子结构和氢转移消除反应。MN和MN~+的HOMO与LUMO能级差(△E(L-H))分别为11.55 eV和7.86 eV,表明MN~+的电子较易被激发;两者的消除反应活化能分别为222.16kJ/mol和115.91 kJ/mol,进一步说明在高能光源辐射作用下,MN将经由MN~+以低能垒的协同过程发生环消除反应,产生的自由基将迅速引发二次反应导致点火和爆炸。
In this paper, the equilibrium geometry, electronic structure and hydrogen transfer elimination reaction of methyl nitrate (MN) and its free radical cation (MN ~ +) were studied by ab initio and MNDO methods. The differences in the energy levels of HOMO and LUMO for MN and MN ~ + are 11.55 eV and 7.86 eV, respectively, indicating that MN ~ + electrons are more easily excited. The activation energies of the two reactions are 222.16 kJ / mol And 115.91 kJ / mol respectively. It is further demonstrated that under the irradiation of high-energy light sources, MN will undergo ring elimination reaction through the synergistic process of MN ~ + with low energy barrier, and the generated radicals will quickly cause secondary reaction to cause ignition and explosion.