Theoretic Studies of the Structures and Properties of Energetic Highnitrogen Compounds 

Author  ZhangChenChen 
Tutor  ZhuWeiHua 
School  Nanjing University of Technology and Engineering 
Course  Physical and chemical 
Keywords  Energetic highnitrogen compounds Density functional theory Heats of formation Detonation properties Bond dissociation energies 
CLC  O621.25 
Type  Master's thesis 
Year  2012 
Downloads  68 
Quotes  0 
The structures and properties of carbonbridged diiminotetrazole derivatives, nitrogenbridged diiminotetrazole derivatives, tetraazaadamantane derivatives, and four nitro or/and nitrate adamantane derivatives were studied systematically using the DFTB3LYP method, and according to the quantitative criteria of energy and stability of a highenergy density compound (HEDC), the potential candidates of HEDCs were selected. Main parts of the study are as follows:1. The structures of five series of carbonbridged diiminotetrazole derivatives were optimized using the B3LYP/631G** method and their single point calculations were performed to obtain their energies of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). The isodesmic reactions of the derivatives were designed to calculate their heats of formation (HOFs). The effects of different substituents and bridges on their HOFs were discussed. Crystal densities of the derivatives were calculated from molecular weight divided by mean molecular volume. Their detonation velocities and pressures were evaluated using the semiempirical KamletJacobs equations. The detonation properties of different derivatives were compared and discussed. The bond dissociation energy (BDE) of each possible thermal trigger bond of all the derivatives was calculated by the UB3LYP/631G** method, and their thermal stabilities were compared.2. The optimizations and the single point calculations were performed to get the energies of the HOMO and LUMO of five series of nitrogenbridged diiminotetrazole derivatives. Their HOFs were calculated via designing isodesmic reactions and the effects of different substituents and nitrogen bridges on their HOFs were discussed. Their crystal densities were estimated from molecular weight divided by mean molecular volume. Their detonation velocities and pressures were evaluated using the semiempirical KamletJacobs equations. The detonation properties of different derivatives were compared and discussed. The BDE of each possible thermal trigger bond of all the derivatives was calculated and compared to judge their thermal stabilities.3. The electronic structural parameters of ten series of tetraazaadamantane derivatives were obtained by the optimizations and the single point calculations. Designing isodesmic reactions were used to estimate their HOFs and the effects of different substituents and their numbers on the HOFs were compared. Crystal densities of the derivatives were calculated via molecular weight divided by mean molecular volume. The semiempirical KamletJacobs equations were used to calculate their detonation velocities and pressures, and their detonation properties were compared and discussed. Each possible thermal trigger bond of all the derivatives was broken to calculate its BDE and their thermal stabilities were compared.4. The structural optimizations and the single point calculations on four nitro or/and nitrate adamantane derivatives were performed to get their electronic structural parameters. The isodesmic reactions of the derivatives were designed to calculate their HOFs. The relative order of their HOFs was compared and discussed. Their crystal densities were estimated from molecular weight divided by mean molecular volume. Their detonation velocities and pressures were evaluated using the semiempirical KamletJacobs equations. The detonation properties of different derivatives were compared and discussed.