Density functional calculations of bond dissociation energies for NO2 scission in some nitroaromatic molecules

Rice, Betsy M.; Sahu, Samir; Owens, Frank J.

doi:10.1016/s0166-1280(01)00782-5

Cited by 265 publications

(207 citation statements)

References 7 publications

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“…Previous studies 18,19 on the BDE for the nitro compounds such as nitroaromatic and nitramine molecules have shown that there is a parallel relationship between the BDE of the weakest R-NO 2 bond scission and the sensitivity. In general, the larger the BDE is, the lower the sensitivity is.…”

Section: Bond Dissociation Energymentioning

confidence: 98%

“…As well known, studies on the bond dissociation energy (BDE) and activation energies (E a ) are important and essential for understanding the decomposition process of the energetic materials, and they are also directly relevant to their thermal stabilities and sensitivities. 4,[18][19][20][21][22][23] Therefore, in this research the BDE and E a of eleven TNAD isomers were calculated and compared at the B3LYP/ 6-31G** and PM3 levels, respectively. Pyrolysis mechanisms and thermal stabilities were estimated from the values of BDE and E a of the initial steps during the decomposition processes.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Studies on Thermolysis Mechanism and Stability of trans‐1,4,5,8‐Tetranitro‐1,4,5,8‐tetraazadecalin Isomers

Qiu

Gong

Xiao³

2008

Chin. J. Chem.

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A systematic study on the thermolysis mechanism and stability of a series of energetic cyclic nitramines, trans-1,4,5,8-tetranitro-1,4,5,8-tetraazadecalin isomers, was performed by density functional theory (DFT) and semiempirical molecular orbital (MO) calculations. Bond dissociation energies (BDE) and activation energies (E a ) of the thermolysis processes were computed at the B3LYP/6-31G** and PM3 levels, respectively. The effect of nitroamino groups on the thermal stability and pyrolysis mechanism of the title compounds was evaluated by the BDE and E a . The correlations among BDE, E a , bond overlap populations, energies of the frontier orbitals, and energy gaps were examined in detail. The results indicate that thermal stabilities and decomposition mechanisms of the title compounds derived from the BDE, E a and static electronic parameters are basically consistent. Homolysis of the N-NO 2 bond is the initial step in the thermolysis of the title compounds, the meta-isomers are more stable than the para-isomers, and the ortho-isomers are the most sensitive.

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Section: Bond Dissociation Energymentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Theoretical Studies on Thermolysis Mechanism and Stability of trans‐1,4,5,8‐Tetranitro‐1,4,5,8‐tetraazadecalin Isomers

Qiu

Gong

Xiao³

2008

Chin. J. Chem.

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“…These two parameters can be calculated by quantum chemical methods [12][13][14][15]. Furthermore, a number of additional parameters such as bond dissociation energies, Mulliken charges and electrostatic potentials, that can provide an indication of the impact sensitivity, can also be computed [16][17][18][19][20]. However, so far no general theory has been established enabling the impact sensitivity to be accurately calculated for a wide range of energetic molecules [21][22][23].…”

Section: Introductionmentioning

confidence: 99%

A Study of the Detonation Properties, Propellant Impulses, Impact Sensitivities and Synthesis of Nitrated ANTA and NTO Derivatives

Jensen

Moxnes

Kjønstad

et al. 2016

Cent. Eur. J. Energ. Mater.

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Nitrated derivatives of 5-amino-3-nitro-1,2,4-triazole (ANTA) and 3-nitro-1,2,4-triazol-5-one (NTO) were theoretically characterized with respect to their performance as high explosives and rocket propellants. The detonation velocity and the detonation pressure of the derivatives, calculated with EXPLO5 software, were at the same level or slightly above the performance of 1,3,5-trinitroperhydro-1,3,5-triazine (RDX). The results showed that compositions of 1,3,4-trinitro-1,2,4-triazol-5-one and glycidyl azide polymer (GAP) could give specific impulses just above 2600 m/s in rocket propellants. The sensitivities of the derivatives were evaluated using their heats of detonation, CHNO-ratios, free space in the crystal lattice and N−NO2 bond dissociation energy. The stability and sensitivity of several of the derivatives could be poor due to the low N−NO2 bond dissociation energies. The N−NO2 bond dissociation energies in the derivatives were calculated to be between 41 and 296 kJ/mol when the M06-2X/6-311+G(2d,p) functional was used. Synthetic routes for the most stable derivatives were proposed. In addition, preliminary studies of the chloride-assisted nitrolysis of NTO were performed. The infrared spectrum of the NTO derivative indicated that N−NO2 bonds were formed.

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“…[26][27][28][29][30] In addition, the sensitivity, which can be used to predict whether an energetic material can be stored safely, was also investigated. Rice and Politzer et al [31][32][33] recently reported that the explosive sensitivity of nitro explosives exhibits a good linear relationship with the bond dissociation energy (BDE) of the trigger bond. These results indicate that the explosive sensitivity of nitro compounds can be evaluated using the BDE of the trigger bond; thus, the BDEs of these derivatives were also evaluated in this study.…”

Section: Introductionmentioning

confidence: 99%

Dft theoretical study of energetic nitrogen-rich C4N6H8-n(NO2)n derivatives

Jin¹,

Hu²,

Jia³

et al. 2014

Quím. Nova

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n (n = 1-6). The heats of formation (HOFs) were calculated by isodesmic reactions, and the detonation properties were evaluated using the Kamlet-Jacobs equations. The bond dissociation energies were also analyzed to investigate the thermal stability and sensitivity of the compounds. The results show that all of the derivatives have high positive HOFs, compound G has the highest theoretical density, and compound F1 has the highest detonation velocity and detonation pressure. Considering both the detonation properties and thermal stabilities, compounds D1 and D4 (3 nitro substituents), E1-E6 (4 nitro substituents), and G (6 nitro substituents) can be regarded as potential candidates for high-energy density materials.

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Density functional calculations of bond dissociation energies for NO2 scission in some nitroaromatic molecules

Cited by 265 publications

References 7 publications

Theoretical Studies on Thermolysis Mechanism and Stability of trans‐1,4,5,8‐Tetranitro‐1,4,5,8‐tetraazadecalin Isomers

Theoretical Studies on Thermolysis Mechanism and Stability of trans‐1,4,5,8‐Tetranitro‐1,4,5,8‐tetraazadecalin Isomers

A Study of the Detonation Properties, Propellant Impulses, Impact Sensitivities and Synthesis of Nitrated ANTA and NTO Derivatives

Dft theoretical study of energetic nitrogen-rich C4N6H8-n(NO2)n derivatives

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