Entity

Time filter

Source Type


Zhu W.,Nanjing University of Science and Technology | Yan Q.,Nanjing University of Science and Technology | Pang A.,Hubai Institute of Aerospace Chemotechnology | Chi X.,Hubai Institute of Aerospace Chemotechnology | And 2 more authors.
Journal of Molecular Modeling | Year: 2014

To improve understanding of the unimolecular decomposition mechanism of 1,2,4-butanetriol trinitrate (BTTN) in the gas phase, density functional theory calculations were performed to determine various decomposition pathways at the B3LYP/6-311G**level. Two main mechanisms for the unimolecular decomposition of BTTN were found. In the first, homolysis of one of the O-NO2 bonds occurs to form •NO2 and CH 2ONO2CHONO2CH2CH2O•, which subsequently decomposes to form CH3CHO + •CHO + 3NO 2 + HCHO. In the second, successive HONO elimination reactions yield three HONO and OHCCH2CHONO2CH2ONO2 fragments, which subsequently decompose to form CH3CHO + 2CO + 3HONO. We also found that the first pathway has a slightly lower activation energy than the second. The results show that the pathway involving O-NO2 cleavage is slightly more energetically favorable than that involving HONO elimination. © 2014 Springer-Verlag.


Yan Q.,Nanjing University of Science and Technology | Zhu W.,Nanjing University of Science and Technology | Pang A.,Hubai Institute of Aerospace Chemotechnology | Chi X.,Hubai Institute of Aerospace Chemotechnology | And 2 more authors.
Journal of Molecular Modeling | Year: 2013

To improve the understanding of the unimolecular decomposition mechanism of nitroglycerin (NG) in the gas phase, density functional theory calculations were performed to determine various decomposition channels at the B3LYP/6-311G**level. For the unimolecular decomposition mechanism of NG, we find two main mechanisms: (I) homolytic cleavage of O-NO2 to form •NO2 and CH2ONO2CHONO 2CH2O•, which subsequently decomposes to form •CHO, •NO2, and 2CH2O; (II) successive HONO eliminations to form HONO and CHO-CO-CHO, which subsequently decomposes to form CH2O + 2CO2 and •CHO + CO. We also find that the former channel has slightly smaller activation energy than the latter one. In addition, the rate constants of the initial process of the two decomposition channels were calculated. The results show that the O-NO2 cleavage pathway occurs more easily than the HONO elimination. © 2012 Springer-Verlag Berlin Heidelberg.

Discover hidden collaborations