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

• 来源期刊: 中国科学B辑（英文版）
• 年，卷（期）: 2008,（5）
• 页码范围: 427-439
• 页数: 13页
• 语种: 英文
• DOI: 10.1007/s11426-008-0058-8

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 -ONO2always 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-, 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.