硫酸自由基与TNT反应的密度泛函理论

A Density Functional Theory of the Reaction of TNT with Sulfate Radical

利用密度泛函理论和Gaussian03程序软件包,研究了硫酸自由基与TNT的反应机理。在B3LYP/6-31G(d)水平下对反应复合物、过渡态和产物进行几何结构的部分优化,并进行振动频率计算,分析了反应过程几何构型的变化和稳定性。实验和计算结果表明,硫酸自由基与TNT的反应主要受动力学控制,氢抽提反应的主反应通道是TNT中甲基氢和硫酸自由基的反应,加成反应主反应通道是TNT苯环上无取代基碳原子和硫酸自由基的反应。

Using the density functional theory （DFT） and Gaussian 03 package software,the reaction mechanism for the TNT with sulfate radical reaction was studied.The geometries of all the molecules reactants,transition states and products were optimized and the harmonic vibration frequencies and the energies were calculated at the level of B3LYP/6-31G（d）.The changes of geometry and stability of reaction process was analyzed.The experimental and calculated results show that the reaction of sulfuric radical with TNT was mainly controlled by dynamics and the major channel of hydrogen abstraction was the reaction of TNT-methyl hydrogen and sulfate radical,meanwhile the major channel of addition reaction was the reaction of non-substituted TNT-phenyl carbon and sulfate radical.