Cu(TO)2(H2O)4](PA)2 was prepared by mixing the aqueous solution of 1,2,4 triazol 5 one(TO) and Cu(PA)2. The molecular structure and crystal structure of the title complex was determined by X ray single crystal diffrac...Cu(TO)2(H2O)4](PA)2 was prepared by mixing the aqueous solution of 1,2,4 triazol 5 one(TO) and Cu(PA)2. The molecular structure and crystal structure of the title complex was determined by X ray single crystal diffraction method. The crystal is triclinic, space group with a=0.7321(1)nm,b=0.7474(2)nm,c=1.3649(3)nm;α=88.65(2)°,β=85.63(1)°,γ=63.35(1)°;V=0.6655(2)nm3,Z=1. The Cu2+ coordinated with two TO molecule through its 2 nitrogen atom and four water molecules and showed an octahedral configuration.展开更多
共价键均裂在含能分子的热分解过程中普遍存在,因此极为重要.然而,以往的理论研究通常用键能(ΔH,BDE)估算均裂能垒,因忽略了熵效应,必然造成较大误差.采用对称破缺密度泛函方法(BS-UB3LYP/6-311+G**),对含能分子3-硝基-1,2,4-三唑-5-酮...共价键均裂在含能分子的热分解过程中普遍存在,因此极为重要.然而,以往的理论研究通常用键能(ΔH,BDE)估算均裂能垒,因忽略了熵效应,必然造成较大误差.采用对称破缺密度泛函方法(BS-UB3LYP/6-311+G**),对含能分子3-硝基-1,2,4-三唑-5-酮(NTO)的热分解机理进行了系统研究和梳理,计算了共价键均裂的过渡态及能垒.结果表明,C—NO_(2)键均裂和随后的自由基复合是最优途径,能垒为216.9 k J·mol^(-1)(523 K).随后产生的NO自由基通过多次“复合-均裂”过程促进三唑中间体开环,分解为HNCO,N_(2)O和CO等小分子,它们相互反应又生成NO_(2),N_(2)和CO_(2).这些分解产物与诸多实验观测结果一致.展开更多
文摘Cu(TO)2(H2O)4](PA)2 was prepared by mixing the aqueous solution of 1,2,4 triazol 5 one(TO) and Cu(PA)2. The molecular structure and crystal structure of the title complex was determined by X ray single crystal diffraction method. The crystal is triclinic, space group with a=0.7321(1)nm,b=0.7474(2)nm,c=1.3649(3)nm;α=88.65(2)°,β=85.63(1)°,γ=63.35(1)°;V=0.6655(2)nm3,Z=1. The Cu2+ coordinated with two TO molecule through its 2 nitrogen atom and four water molecules and showed an octahedral configuration.
文摘共价键均裂在含能分子的热分解过程中普遍存在,因此极为重要.然而,以往的理论研究通常用键能(ΔH,BDE)估算均裂能垒,因忽略了熵效应,必然造成较大误差.采用对称破缺密度泛函方法(BS-UB3LYP/6-311+G**),对含能分子3-硝基-1,2,4-三唑-5-酮(NTO)的热分解机理进行了系统研究和梳理,计算了共价键均裂的过渡态及能垒.结果表明,C—NO_(2)键均裂和随后的自由基复合是最优途径,能垒为216.9 k J·mol^(-1)(523 K).随后产生的NO自由基通过多次“复合-均裂”过程促进三唑中间体开环,分解为HNCO,N_(2)O和CO等小分子,它们相互反应又生成NO_(2),N_(2)和CO_(2).这些分解产物与诸多实验观测结果一致.
