Journal of Molecular Modeling

, 23:269 | Cite as

A density functional theory study of the decomposition mechanism of nitroglycerin

  • Liguan Pei
  • Kehai Dong
  • Yanhui Tang
  • Bo Zhang
  • Chang Yu
  • Wenzuo Li
Original Paper


The detailed decomposition mechanism of nitroglycerin (NG) in the gas phase was studied by examining reaction pathways using density functional theory (DFT) and canonical variational transition state theory combined with a small-curvature tunneling correction (CVT/SCT). The mechanism of NG autocatalytic decomposition was investigated at the B3LYP/6-31G(d,p) level of theory. Five possible decomposition pathways involving NG were identified and the rate constants for the pathways at temperatures ranging from 200 to 1000 K were calculated using CVT/SCT. There was found to be a lower energy barrier to the β-H abstraction reaction than to the α-H abstraction reaction during the initial step in the autocatalytic decomposition of NG. The decomposition pathways for CHOCOCHONO2 (a product obtained following the abstraction of three H atoms from NG by NO2) include O–NO2 cleavage or isomer production, meaning that the autocatalytic decomposition of NG has two reaction pathways, both of which are exothermic. The rate constants for these two reaction pathways are greater than the rate constants for the three pathways corresponding to unimolecular NG decomposition. The overall process of NG decomposition can be divided into two stages based on the NO2 concentration, which affects the decomposition products and reactions. In the first stage, the reaction pathway corresponding to O–NO2 cleavage is the main pathway, but the rates of the two autocatalytic decomposition pathways increase with increasing NO2 concentration. However, when a threshold NO2 concentration is reached, the NG decomposition process enters its second stage, with the two pathways for NG autocatalytic decomposition becoming the main and secondary reaction pathways.


Nitroglycerin (NG) Density functional theory (DFT) Canonical variational transition state theory (CVT) Autocatalytic decomposition Rate constant 



This work was supported by Yantai University’s laboratory, led by Dr. Wenzuo Li—especially the investigation that used the Gaussian 09 software package.


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Copyright information

© Springer-Verlag GmbH Germany 2017

Authors and Affiliations

  • Liguan Pei
    • 1
  • Kehai Dong
    • 1
  • Yanhui Tang
    • 1
  • Bo Zhang
    • 1
  • Chang Yu
    • 1
  • Wenzuo Li
    • 2
  1. 1.Department of Aircraft EngineeringNaval Aeronautical Engineering UniversityYantai CityChina
  2. 2.College of Chemistry and Chemical EngineeringYantai UniversityYantaiChina

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