Mechanisms of gas phase decomposition of C-nitro compounds from quantum chemical data

Храпковский, Г. М.; Шамов, А. Г.; Николаева, Е. В.; Чачков, Д. В.

doi:10.1070/rc2009v078n10abeh004053

Cited by 48 publications

(19 citation statements)

References 3 publications

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“…As can be seen, the reaction (4) has a chemical endothermicity (∆E) of 70-93 kJ/mol, and the BMK (77.6 kJ/mol), M06-2X (73.6 kJ/mol), and G4 (75.5 kJ/mol) results are in good agreement with experimental value [44] of 75.3 kJ/mol. The calculated activation energy at the M06-2X level agrees reasonably well with the experimental result [45] (188.5 kJ/mol), and the absolute deviation from experiment is less than 7 kJ/mol. The B3LYP calculated result is about 10 kJ/mol lower than experimental prediction.…”

Section: Pathway IIsupporting

confidence: 78%

“…As can be seen from Table 2, TS2 for the nitro to nitrite rearrangement of NE is calculated to be 253-290 kJ/mol (reference value [45] of 272-277 kJ/mol) in energy above parent NE, which is averagely about 18 kJ/mol higher than BDE(C-NO 2 ) of NE, and hence the rearrangement reaction of NE will strongly compete with direct rupture of the C-NO 2 bond. It is worth to note that, in a similar way to the CME reaction of NE, the rearrangement of nitro to nitrite is also a non-radical process.…”

Section: Pathway IIImentioning

confidence: 99%

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Understanding the Initial Decomposition Pathways of the n‐Alkane/Nitroalkane Binary Mixture

Guan

Zhang

et al. 2013

Chin. J. Chem.

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Addition of nitroalkanes into n-alkanes can lower the activation barriers of free-radical production and accelerate the decomposition of n-alkanes at relatively low temperatures. Four initial decomposition mechanisms of the n-butane/nitroethane binary mixture were proposed for the promoting effect and considered theoretically at the B3LYP, BB1K, BMK, MPW1K, and M06-2X levels with MG3S basis set. Energetics above was compared to high-level CBS-QB3 and G4 calculations. Calculated results confirm the feasibility of the four initial decomposition pathways: (I) the C-NO 2 bond rupture of nitroethane to produce ethyl and •NO 2 , (II) HONO elimination from nitroethane followed by decomposition to •OH and •NO, (III) rearrangement of nitroethane to ethyl nitrite which further dissociates into CH 3 CH 2 O• and •NO, and (IV) direct hydrogen-abstraction of nitroethane with n-butane.

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Section: Pathway IIsupporting

confidence: 78%

Section: Pathway IIImentioning

confidence: 99%

Understanding the Initial Decomposition Pathways of the n‐Alkane/Nitroalkane Binary Mixture

Guan

Zhang

et al. 2013

Chin. J. Chem.

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“…Shamov and Khrapkovskii considered the pyrolysis mechanism of nitroethylene through B3LYP/6-31G(d) functional [12]. Khrapkovskii and Shamov reviewed quantum chemical data on gas-phase decomposition mechanisms of C-nitro compounds including nitroethylene [13].…”

Section: Introductionmentioning

confidence: 99%

Electronic spectra of nitroethylene

Borges

Barbatti

Aquino

et al. 2011

Int J of Quantum Chemistry

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A systematic study of the electronic excited states of nitroethylene (C₂H₃NO₂) was carried out using the approximate coupled-cluster singles-and-doubles approach with the resolution of the identity (RI-CC2), the time dependent density functional theory with the CAMB3LYP functional (TDDFT/CAMB3LYP) and the DFT multireference configuration interaction (DFT/MRCI) method. Vertical transition energies and optical oscillator strengths were computed for a maximum of 20 singlet transitions. Semiclassical simulations of the ultraviolet (UV) spectra were performed at the RI-CC2 and DFT/MRCI levels. The main features in the UV spectrum were assigned to a weak n-π* transition, and two higher energy π_CC+O−π* bands. These characteristics are common to molecules containing NO2 groups. Simulated spectra are in good agreement with the experimental spectrum. The energy of the bands in the DFT/MRCI simulation agrees quite well with the experiment, although it overestimates the band intensities. RI-CC2 produced intensities comparable to the experiment, but the bands were blue shifted. A strong π_CC+O−π* band, not previously measured, was found in the 8–9 eV range

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“…Model 2 considers the first order reaction kinetics, taking into account the presence of two steps in the transformation of compound А 1 into isomer А 2 to give stable intermediate B. This reaction mechanism is suggested for the nitro-nitrate rearrangement of nitroalkanes and for isomerization of nitroalkanes having two H atoms in the α position to the nitro group [1,2]. In this case, the following equations hold for the early stage of the process:…”

Section: (3)mentioning

confidence: 99%

“…In recent years, the structure and properties of iso mers of some explosives have been studied by mathe matical modeling [1][2][3][4][5]. The dependences of the acti vation energy of thermal decomposition of explosives on the isomer structures have been elucidated, the pos sibility of isomer interconversion has been demon strated, and the energy barriers to isomerization have been determined for different isomerization mecha nisms.…”

mentioning

confidence: 99%

The effect of isomerization of reactant molecules on the early stage of chemical reaction kinetics

2013

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Mechanisms of gas phase decomposition of C-nitro compounds from quantum chemical data

Cited by 48 publications

References 3 publications

Understanding the Initial Decomposition Pathways of the n‐Alkane/Nitroalkane Binary Mixture

Understanding the Initial Decomposition Pathways of the n‐Alkane/Nitroalkane Binary Mixture

Electronic spectra of nitroethylene

The effect of isomerization of reactant molecules on the early stage of chemical reaction kinetics

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