Theoretical studies on new potential high energy density compounds (HEDCs) adamantyl nitrates from gas to solid  

作　　者：XU XiaoJuan ZHU WeiHua GONG XueDong XIAO HeMing 

机构地区：[1]Department of Chemistry,Nanjing University of Science and Technology,Nanjing 210094,China [2]Department of Chemistry,Yancheng Teacher’s College,Yancheng 224002,China

出　　处：《Science China Chemistry》2008年第5期427-439,共13页中国科学（化学英文版）

基　　金：the National Natural Science Foundation of China (Grant Nos. 10576016 and 10576030);the National 973 Project

摘　　要：A series of adamantyl nitrates have been theoretically studied from gas to solid to search for new po-tential high energy density compounds (HEDCs). The heats of formation (HOFs) for the 26 title com-pounds were calculated by designing isodesmic reactions at the B3LYP/6-31G level. It was found that the HOFs of the 26 isomers with the same number of —ONO2 groups (n) are not correlated well with the corresponding substituted positions. According to the obtained heats of detonation (Q),detonation velocities (D),and detonation pressures (P) using the Kamlet-Jacobs equations,it was found that when n=7～8,the adamantyl nitrates meet the criterion as an HEDC. The calculations on bond dissociation energies of O—N (EO—N) showed that the adamantyl nitrates with gemi —ONO2 always have the worst stability among the isomers,and all the adamantyl nitrates with gemi —ONO2 have similar stability. Due to the complexity of their structures,values of EO—N do not decrease with the increase of the substituent number n obviously,and the stability of adamantyl nitrates is not determined by only one structural parameter. Considering the stability requirement,only 1,2,4,6,8,9,10-adamantyl heptanitrate is recom-mended as a feasible HEDC. Molecular packing searching for 1,2,4,6,8,9,10-adamantyl heptanitrate among 7 most possible space groups (P21/c,P-1,P212121,P21,Pbca,C2/c,and Pna21) using Compass and Dreiding force fields showed that this compound tends to crystallize in P21/c. Ab initio periodic calculations on the electronic structure of the predicted packing showed that the O—NO2 bond is the trigger bond during thermolysis,which agrees with the result derived from the study of dissociation energies of O—N bonds.A series of adamantyl nitrates have been theoretically studied from gas to solid to search for new potential high energy density compounds (HEDCs). The heats of formation (HOFs) for the 26 title compounds were calculated by designing isodesmic reactions at the B3LYP/6-31G* level. It was found that the HOFs of the 26 isomers with the same number of -ONO2 groups (n) are not correlated well with the corresponding substituted positions. According to the obtained heats of detonation (Q), detonation velocities (D), and detonation pressures (P) using the Kamlet-Jacobs equations, it was found that when n=7～8, the adamantyl nitrates meet the criterion as an HEDC. The calculations on bond dissociation energies of O-N (E O-N) showed that the adamantyl nitrates with gemi- ONO2 always have the worst stability among the isomers, and all the adamantyl nitrates with gemi- ONO2 have similar stability. Due to the complexity of their structures, values of E O-N do not decrease with the increase of the substituent number n obviously, and the stability of adamantyl nitrates is not determined by only one structural parameter. Considering the stability requirement, only 1,2,4,6,8,9,10-adamantyl heptanitrate is recommended as a feasible HEDC. Molecular packing searching for 1,2,4,6,8,9,10-adamantyl heptanitrate among 7 most possible space groups (P21/c, P-1, P212121, P21, Pbca, C2/c, and Pna21) using Compass and Dreiding force fields showed that this compound tends to crystallize in P21/c. Ab initio periodic calculations on the electronic structure of the predicted packing showed that the O-NO2 bond is the trigger bond during thermolysis, which agrees with the result derived from the study of dissociation energies of O-N bonds.

关 键 词：high energy DENSITY compound (HEDC) adamantyl NITRATE molecular PACKING periodic calculation ENERGETIC property DENSITY of STATES (DOS) 

分 类 号：O611.3[理学—无机化学]