Structure and energetic properties of 1,5-dinitrobiuret

Suntsova, Marina A.; Marochkin, Ilya I.; Дорофеева, О. В.

doi:10.1007/s11224-012-0176-y

Cited by 10 publications

(12 citation statements)

References 24 publications

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“…Density functional theory (DFT) [13,14] has emerged as a very reliable and economical tool to predict the chemical and physical properties of unknown energetic materials. The B3LYP/6-31G (d,p) basis set, which can not only produce reliable geometries and energies, but also require less time and computer resources, was used to compute the title compounds on a Gaussian 03 package [15].…”

Section: Methodsmentioning

confidence: 99%

Theoretical studies on two novel series of energetic cyclic nitramines

Jin

Liu

2014

Struct Chem

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Density functional theory calculations at the B3LYP/6-31G** theoretical level were performed for two series of guanidine-fused bicyclic skeleton derivatives (B-B7 and C-C7). The heats of formation (HOFs) were calculated via isodesmic reaction; the detonation properties were evaluated using the Kamlet-Jacobs equations; the bond dissociation energies were also analyzed to investigate the thermal stability of the cyclic nitramines. The results show that all the derivatives have high positive HOFs; compounds containing -N 3 groupshave the highest HOFs, while compounds containing -NF 2 groups have the highest density and detonation properties. Taking both of the detonation properties and thermal stabilities into consideration, compounds B1, B2, B5, C3, and C5 can be considered as the potential candidate of high-energy density compounds.

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Section: Methodsmentioning

confidence: 99%

Theoretical studies on two novel series of energetic cyclic nitramines

Jin

Liu

2014

Struct Chem

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“…The electronic structure of DNB was recently studied by Dorofeeva et al 29 by two-dimensional B3LYP potential energy scans. They reported two low-energy conformers, named as pseudo-trans (C s ) and pseudo-cis (C 2 ), which differed in energy by 1.8 kcal/mol from the G4 calculations.…”

Section: A Molecular Structures Of Mnb and Dnbmentioning

confidence: 99%

“…The DNB (C 2v ) to DNB (C s ) transformation can be achieved by a two-step rotation mechanism 6 as illustrated in Figure 7, rather than by a single rotation step. 29 It can proceed by rotation of the C-NHNO 2 bond via TS9 to the DNB (C 1 ) conformer and then by rotation of the N-CONHNO 2 bond via TS10. However, we note that fast equilibrium between the two DNB conformers is not likely due to the need for multiple rotations, which require overcoming higher barriers and larger entropy changes compared to the case present in MNB.…”

Section: Ab Initio Kinetics Of Dnb Thermal Decompositionmentioning

confidence: 99%

Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

Sun

Vaghjiani

2015

The Journal of Chemical Physics

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Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH2 group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C2v symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice-Ramsperger-Kassel-Marcus/multi-well master equation simulations, the results of which reveal the formation of (NO2 + H2O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358-366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.

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“…Next, Suntsova et al [24] describe the use of density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2) to estimate stable conformers of 1,5-dinitrobiuret (DNB) in the gaseous state. The enthalpy of formation of gaseous DNB was determined to be -257 ± 5 kJ mol -1 and that of crystal DNB was -415 ± 15 kJ mol -1 .…”

Section: Issuementioning

confidence: 99%

Interplay of thermochemistry and structural chemistry, the journal (volume 24, 2013, issues 3–4) and the discipline

et al. 2014

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The contents of issues 3 and 4 for the calendar year 2013 are summarized in the current review of the journal Structural Chemistry. A brief thermochemical commentary is added to the summary of each paper. Abbreviations AIM Atoms in molecules BNNT Boron nitride nanotube CNC Carbon nanocone CSD Crystal structure determination DFT Density functional theory DNB 1,5-Dinitrobiuret EDA Energy decomposition analysis HF Hartree-Fock GED Gas electron diffraction GIAO Gauge-independent atomic orbital HOMA Harmonic oscillator measure of aromaticity MD Molecular dynamics MP Møller-Plesset perturbation MP2Second-order Møller-Plesset perturbation NRT Natural resonance theory ONIOM Our own N-layered integrated molecular orbital and molecular mechanics QTAIM Quantum theory of atoms-in-molecules NAO Natural atomic orbital NBO Natural bond orbital PES Potential energy surface

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Structure and energetic properties of 1,5-dinitrobiuret

Cited by 10 publications

References 24 publications

Theoretical studies on two novel series of energetic cyclic nitramines

Theoretical studies on two novel series of energetic cyclic nitramines

Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

Interplay of thermochemistry and structural chemistry, the journal (volume 24, 2013, issues 3–4) and the discipline

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