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DFT Studies on Detonation Properties, Pyrolysis Mechanism, and Stability of the Nitro and Hydroxyl Derivatives of Benzene
Author(s) -
Du Hongchen,
Liu Hui,
Liu Yan,
Zhang Jianyinga,
Wang Fang,
Gong Xuedong
Publication year - 2011
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.201190104
Subject(s) - chemistry , bond dissociation energy , nitro , detonation , benzene , computational chemistry , hydrogen bond , pyrolysis , density functional theory , dissociation (chemistry) , molecule , organic chemistry , explosive material , alkyl
Ninety‐one nitro and hydroxyl derivatives of benzene were studied at the B3LYP/6‐31G∗ level of density functional theory. Detonation properties were calculated using the Kamlet‐Jacobs equation. Three candidates (pentanitrophenol, pentanitrobenzene, and hexanitrobenzene) were recommended as potential high energy density compounds for their perfect detonation performances and reasonable stability. The pyrolysis mechanism was studied by analyzing the bond dissociation energy (BDE) and the activation energy ( E a ) of hydrogen transfer (H–T) reaction for those with adjacent nitro and hydroxyl groups. The results show that E a is much lower than BDEs of all bonds, so when there are adjacent nitro and hydroxyl groups in a molecule, the stability of the compound will decrease and the pyrolysis will be initiated by the H–T process. Otherwise, the pyrolysis will start from the breaking of the weakest C–NO 2 bond, and only under such condition, the Mulliken population or BDE of the C–NO 2 bond can be used to assess the relative stability of the compound.