Crystal structure, detonation performance, and thermal stability of a new polynitro cage compound: 2, 4, 6, 8, 10, 12, 13, 14, 15-nonanitro-2, 4, 6, 8, 10, 12, 13, 14, 15-nonaazaheptacyclo [5.5.1.13, 11. 15, 9] pentadecane

Zhang, Jianying; Du, Hongchen; Wang, Fang; Gong, Xuedong; Ying, Sanjiu

doi:10.1007/s00894-011-1259-1

Cited by 19 publications

(4 citation statements)

References 49 publications

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“…Additionally, in the case of TEX ( 2 ), we were able to calculate the Δ f H gas 0 directly at the W1-F12 level without resorting to isodesmic reactions. Note that the resulting value Δ f H gas 0 = −95.6 ± 1.5 kcal mol –1 , which is again ∼12 kcal mol –1 higher than the best DFT estimations reported so far . In Table , we summarized all of the most important quantitative thermochemical data of CL-20, TEX, and ONC obtained in this work.…”

Section: Resultsmentioning

confidence: 99%

Accurate Prediction of Bond Dissociation Energies and Barrier Heights for High-Energy Caged Nitro and Nitroamino Compounds Using a Coupled Cluster Theory

Kiselev

Goldsmith

2019

J. Phys. Chem. A

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Highly accurate theoretical values of bond energies and activation barriers of primary decomposition reactions are crucial for reliable predictions of thermal decomposition and detonation-related phenomena of energetic materials (EM). However, due to the prohibitive computational cost, high-level ab initio calculations had been impractical for a large number of important EMs, including, e.g., hexanitrohexaazaisowurtzitane (CL-20). In the present work, we obtained accurate bond dissociation energies and the activation barriers for primary decomposition reactions for a series of novel promising caged polynitroamino and polynitro EMs, viz., CL-20, TEX, octanitrocubane (ONC), and hexanitro derivatives of adamantane, using the recently proposed domain-localized pair natural orbitals (DLPNO) modifications of coupled cluster techniques. DLPNO-CCSD(T) allows for routine quadruple-ζ basis set quality coupled cluster calculations for the species comprised of ∼30 non-H atoms. The benchmarks on a number of simpler congeners of CL-20 and ONC revealed that the DLPNO approach does not deteriorate the quality of the quadruple-ζ coupled cluster procedure. With the aid of this technique, the full set of gas-phase primary decomposition reactions for all 9 conformers of CL-20 was considered. For all species studied, C−NO 2 or N−NO 2 radical decomposition channels dominate over molecular counterparts. The best theoretical results reported in the literature so far, viz., density functional theory energies of nitro group radical elimination in CL-20 and ONC, underestimate the value by ∼10 kcal mol −1 . We also present reliable and accurate gas-phase formation enthalpies for CL-20, ONC, and related species. In a more general sense, these results offer a new level of predictive computational kinetics for polynitro-caged energetic materials.

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Section: Resultsmentioning

confidence: 99%

Accurate Prediction of Bond Dissociation Energies and Barrier Heights for High-Energy Caged Nitro and Nitroamino Compounds Using a Coupled Cluster Theory

Kiselev

Goldsmith

2019

J. Phys. Chem. A

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“…ΔH o f is one of the most important thermodynamic data for compounds, especially essential in evaluating detonation property for explosives. Of the several methods that have been shown to predict reliable values in the literature, [12][13][14][15][24][25][26][27][28][29][30][31][32][33][34][35][36][37] formation reaction, atomization reaction, and isodesmic reaction were used respectively during the present study. In brief, the gas phase ΔH o f cubane can be computed as…”

Section: Methodsmentioning

confidence: 99%

Comparison of theoretical methods via different ways for assessing the heat of formation of cubane

Zhang

Chen

Wang

et al. 2023

J of Physical Organic Chem

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Four ways are introduced for the comparative prediction on solid phase heat of formation ΔHof (s) of cubane through different level of theories (B3LYP/6‐31G(d,p), B3LYP/6‐311+G(2d,2p), B3PW91/6‐31G(d,p), MP2/6‐31G(d,p), and G2). It is based on the heats of sublimation ΔHsub derived from information obtained from the quantum‐mechanically calculated electrostatic potential of each isolated molecule. The ΔHsub are combined with the aforementioned gas phase heats of formation ΔHof (g) to produce condensed phase heats of formation ΔHof (s). Comparisons of the methods are given, along with the recommendations about the methods that could produce better agreement with experiment, wishing to offer some beneficial references.

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“…[5][6][7][8] Some of the recent reports on high energetic materials outline that nitramine materials play an important role in aeronautics, weapons industry and other high tech fields in science and technology as it contains one or more covalently bonded NZNO 2 groups at different valance states. [9][10][11] The most interesting characteristic feature of nitramines is the configuration of the bonds formed by the amine nitrogen atom in the molecule; some of the reported nitramine compounds are RDX, [12] CL-20, [13] HMX, [14] etc., and these are today's well-known explosives. Nitramines are the nitro group substituted ammonia compounds, which are the common substituent in high energy density materials [15][16][17]; in which, the compounds with nitro groups having high energy content can be used as propellants and explosives.…”

Section: Introductionmentioning

confidence: 99%

Probing the effect of nitro groups in nitramine based energetic molecules: a DFT and charge density study

Kandhakumar

Jothi

Kumaradhas

2015

Molecular Simulation

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The structure, electron density distribution, energetic and electrostatic properties of simple nitramine based energetic TMA, DMNA, MDA and TNA molecules were determined using density functional theory (B3LYP) with the 6-311G** and augcc-pVDZ basis sets coupled with Bader's theory of atoms in molecules. In the NO 2 group substituted molecules, the NZN bond distance increases with the increase of NO 2 groups, whereas in CZN bonds, this effect is relatively less, and the distances are almost equal. The topological analysis of electron density reveals that the electron density r bcp (r) of CZN and NZN bonds are significantly decreasing with the increase of NO 2 groups in the nitramine molecules. The Laplacian of electron density f 2 r bcp (r) of NZNO 2 bonds [DMNA: 2 16.7 eÅ 25 , MDA: 212.8 eÅ 25 and TNA: 27.9 eÅ 25 ] of the molecules are relatively less negative, and the values also decrease with the increase of NO 2 groups; this implies that the charge concentration decreases with the increase of NO 2 groups, which leads to weakening the NZN bonds of the molecules. The isosurface of molecular electrostatic potential displays high electronegative regions around the NO 2 groups. The oxygen balance OB 100 of the molecules increases as the number of NO 2 group increases in the molecules, in which, the TNA molecule having maximum OB 100 value [þ7.89]. The band gap, heat of detonation, bond dissociation energy and charge imbalance are predominantly depends on the number of NO 2 group present in the molecule. The charge imbalance parameter (n) has been calculated for all molecules, which reveals that TNA is a highly sensitive molecule, the corresponding n value is 0.047.

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Crystal structure, detonation performance, and thermal stability of a new polynitro cage compound: 2, 4, 6, 8, 10, 12, 13, 14, 15-nonanitro-2, 4, 6, 8, 10, 12, 13, 14, 15-nonaazaheptacyclo [5.5.1.13, 11. 15, 9] pentadecane

Cited by 19 publications

References 49 publications

Accurate Prediction of Bond Dissociation Energies and Barrier Heights for High-Energy Caged Nitro and Nitroamino Compounds Using a Coupled Cluster Theory

Accurate Prediction of Bond Dissociation Energies and Barrier Heights for High-Energy Caged Nitro and Nitroamino Compounds Using a Coupled Cluster Theory

Comparison of theoretical methods via different ways for assessing the heat of formation of cubane

Probing the effect of nitro groups in nitramine based energetic molecules: a DFT and charge density study

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