Stability,detonation properties and pyrolysis mechanisms of polynitrotriprismanes C_6H_(6-n)(NO_2)_n (n=1-6)  

作　　者：唐忠海 欧阳永中 梁逸曾 饶力群 

机构地区：[1]School of Chemistry and Chemical Engineering,Research Center of Modernization of Chinese Medicines,Central South University [2]College of Bioscience and Biotechnology,Hunan Agriculture University

出　　处：《Journal of Central South University》2011年第5期1395-1401,共7页中南大学学报（英文版）

基　　金：Projects(2006DFA41090,2007DFA40680) supported by the International Cooperation Project on Traditional Chinese Medicines of Ministry of Science and Technology of China;Project(20475066) supported by the National Natural Science Foundation of China

摘　　要：To further test whether polynitriprismanes are capable of being potential high energy density materials （HEDMs）, extensive theoretical calculations were carried out to investigate on a series of polynitrotriprismanes （PNNPs）： C6H6-.（NO2）. （n=1-6） Heats of formation （HOFs）, strain energies （SE）, and disproportionation energy （DE） were obtained using B3LYP/6-311＋G（2df, 2p）//B3LYP/6-31G＊ method by designing different isodesmic reactions, respectively. Detonation properties of PNNPs were obtained by the well-known KAMLET-JACOBS equations, using the predicted densities （p） obtained by Monte Carlo method and HOFs. It is found that they increase as the number of nitro groups n varies from 1 to 6, and PNNPs with n〉4 have excellent detonation properties The relative stability and the pyrolysis mechanism of PNNPs were evaluated by the calculated bond dissociation energy （BDE）. The comparison of BDE suggests that rupturing the C--C bond is the trigger for thermolysis of PNNPs. The computed BDE for cleavage of C--C bond （88.5 kJ/mol） further demonstrates that only the hexa-nitrotriprismane can be considered to be the target of HEDMs.To further test whether polynitriprismanes are capable of being potential high energy density materials (HEDMs),extensive theoretical calculations were carried out to investigate on a series of polynitrotriprismanes (PNNPs):C6H6-n(NO2)n (n=1-6).Heats of formation (HOFs),strain energies (SE),and disproportionation energy (DE) were obtained using B3LYP/6-311+G(2df,2p)//B3LYP/6-31G method by designing different isodesmic reactions,respectively.Detonation properties of PNNPs were obtained by the well-known KAMLET-JACOBS equations,using the predicted densities (ρ) obtained by Monte Carlo method and HOFs.It is found that they increase as the number of nitro groups n varies from 1 to 6,and PNNPs with n 4 have excellent detonation properties.The relative stability and the pyrolysis mechanism of PNNPs were evaluated by the calculated bond dissociation energy (BDE).The comparison of BDE suggests that rupturing the C-C bond is the trigger for thermolysis of PNNPs.The computed BDE for cleavage of C-C bond (88.5 kJ/mol) further demonstrates that only the hexa-nitrotriprismane can be considered to be the target of HEDMs.

关 键 词：high energy density materials polynitrotriprismanes heats of formation strain energies disproportionation energy bond dissociation energy 

分 类 号：O642[理学—物理化学]