摘要
结合密度泛函理论和微扰理论,选用6-311++G(d,p)和6-311++G(2df,2p)基组,系统研究了3,5-二硝基-1,2,4-三唑(DNTz)及其复合物(MDNTz,M为H+,Li+,Na+,K+,Be2+以及Mg2+)的热引发键C—NO2键长(d)、解离能(BDEC3—N7)、相互作用能(Eint)、电子云密度(ρBCP(C3—N7))、离域化能E(2)和硝基电荷(qNO2)对感度的影响。结果表明,BDEC3—N7与dC3—N7成线性关系;ΔBDEC3—N7与qNO2、E(2)、ρBCP(C3—N7)以及自然键轨道(NBO)电荷转移量均成线性关系;感度顺序为DNTz…Be2+<DNTz…Mg2+<DNTz…H+<DNTz…Li+<DNTz…Na+<DNTz…K+。分子原子理论(AIM)和NBO分析表明,DNTz中的硝基与金属离子产生相互作用,体系的共轭关系被打破,增加了C3—N7键强度,使其感度降低。
Based on Density functional theory(DFT)and Mechanical Perturbation theory(MP2(full)),two basis sets of 6-311++G(d,p)and 6-311++G(2df,2p)are used to study the change of bond length(d),bond dissociation energy(BDE)of trigger bond(C3—NO2),interactional energies and nitro charge in DNTz and its complexes(H+,Li+,Na+,K+,Be2+or Mg2+).There is a linear relationship between the bond dissociation energy of the C3—N7 trigger bond and the molecule-cation interaction energy(Eint),natural charge of the nitro group,electron densityρBCP(C3—N7),delocalization energy E(2)as well as NBO charge transfer,showing that the sensitivity of the complexes follows the order of DNTz…Be2+<DNTz…Mg2+<DNTz…Li+<DNTz…Na+<DNTz…K+.The results of AIM and NBO demonstrate that the nitro group in DNTz interacts with metal ions,and the conjugation of the system is broken,strengthening the trigger bond of C3—N7,and reducing the sensitivity of DNTz.
作者
朱佳平
ZHU Jiaping(Department of Applied Chemistry, Guangdong University of Petrochemical Technology, Maoming 525000, China)
出处
《广东石油化工学院学报》
2020年第3期19-24,共6页
Journal of Guangdong University of Petrochemical Technology
基金
广东石油化工学院科研基金项目(519015)。
关键词
DNTz
引发键
解离能
硝基电荷
密度泛函理论
DNTz
trigger bond
bond dissociation energy
nitro group charge
density functional theory
