电场效应对硝酸羟胺离子间相互作用影响的密度泛函研究

Density Functional Theory Study on the Influence of Electric Field on Hydroxylamine Nitrate

为了研究硝酸羟胺基推进剂电点火过程中的电场效应对推进剂的影响，采用DFT—B3LYP／6-311＋＋G（d，P）方法，对硝酸羟胺的几何构型进行优化。通过自然键轨道分析揭示了氢键作用的本质。对构型形成过程中H原子转移进行了理论研究。在-0．005～0．005a．u．外电场强度下计算了H原子转移的过渡态构型和活化能垒，并对氢键作用的键长、结合能以及能级分布随电场的变化进行了计算。结果表明，随着正向电场的增强，H原子转移活化能垒逐渐减小，有利于硝酸羟胺构型的形成。硝酸羟胺氢键作用键长缩短，键的强度增强。结合能增加，硝酸羟胺的稳定性增强。点火过程中的电场效应对硝酸羟胺的极化或者电离产生负面影响，不利于推进剂的点火。

To study the influence of the electric field produced in the electric ignition process of hydroxylamine nitrate base propellant on the propellant, the geometric configuration of hydroxylamine nitrate was optimized by the B3LYP/6-311 ＋＋G （d, p） method. The nature of the hydrogen bonding interaction was revealed by the analysis of the natural bond orbital. The theoretical study of H atom transfer in the process of configuration formation was performed. Under the external electric fields ranging from -0. 005 a. u. to O. OOS a. u. , the configurations of transition states and activation barrier of H atom transfer were calculated. The change in bond length, binding energy and bond level distribution of hydrogen bonding interaction with the electric field were calculated Results show that with the enhancement of positive electric field, the activation barrier of H atom transfer decreases gradually, it is conducive to the formation of the hydroxylarnine nitrate configuration. The bond length of hydrogen bonding interaction of hydroxylamine nitrate shortens, the strength of the bond enhances. The binding energy of hydroxylamine nitrate increases, the stability of hydroxylamine nitrate enhances. The electric field effect in the ignition process has a negative impact on the polarization or ionization of hydroxylarnine nitrate, which is not conducive to the ignition of the propellant.