Experimental and Theoretical Study on the Structure of Nitramide H<sub>2</sub>NNO<sub>2</sub>

Häußler, Angelika; Klapötke, Thomas M.; Piotrowski, Holger

doi:10.1515/znb-2002-0204

Cited by 15 publications

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“…The UV absorption spectrum of nitramide has been obtained in the crystal, in the solution, ,3a and in the gas phase 3b. The gas-phase spectrum exhibits a moderate band centered around 6.3 eV.…”

Section: Introductionmentioning

confidence: 99%

“…Additionally, the solution spectrum presents two weak shoulders under 5.0 eV . The theoretical assignment has been accomplished by several authors − by using different theoretical approaches. Both Stals et al .…”

Section: Introductionmentioning

confidence: 99%

“…From that point on, the most probable dissociation mechanism is determined by considering relative energies among the different stationary points and the major role played by conical intersections connecting S 3 /S 2 , S 2 /S 1 , and S 1 /S 0 electronic states. The most likely dissociation products are NH 2 (1 2 B 1 ), NO 2 (1 2 A 1 ), NO 2 (1 2 A 2 ), NO 2 (1 2 B 2 ), NO 2 (1 2 A 1 )*, NH 2 NO(1A‘ ‘), NO(XΠ), and O( 1 D). With regards to the influence of triplet states in the photodecomposition of nitramide, our calculations indicate that T 1 /S 0 crossing is probable only after radiationless deactivation.…”

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Photodissociation Mechanism of Nitramide: A CAS-SCF and MS-CASPT2 Study

et al. 2005

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The complete active space self-consistent field (CAS-SCF) method combined with the multistate second-order perturbation theory (MS-CASPT2) are used to study the low-lying, singlet and triplet, potential energy surfaces of nitramide. Vertical transition calculations have allowed us to reinterpret the gas-phase UV spectrum of nitramide as the overlapping of two intense bands calculated at 6.46 and 6.52 eV, respectively. The states of relevance in its photochemistry after excitation at different wavelengths have been determined to be up to S4. From that point on, the most probable dissociation mechanism is determined by considering relative energies among the different stationary points and the major role played by conical intersections connecting S3/S2, S2/S1, and S1/S0 electronic states. The most likely dissociation products are NH2(1(2)B1), NO2(1(2)A1), NO2(1(2)A2), NO2(1(2)B2), NO2(1(2)A1)*, NH2NO(1(1)A''), NO(X(2)pi), and O(1D). With regards to the influence of triplet states in the photodecomposition of nitramide, our calculations indicate that T1/S0 crossing is probable only after radiationless deactivation.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Photodissociation Mechanism of Nitramide: A CAS-SCF and MS-CASPT2 Study

et al. 2005

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“…In addition, it was found that under acidic conditions the N ‐alkyl nitramines, RHNNO 2 , undergo the same type of decomposition reaction as the parent nitramine, but not under basic conditions. Also, nitramines and their catalyzed decomposition reactions have been the subjects of several computational studies …”

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confidence: 99%

Protonation of Nitramines: Where Does the Proton Go?

2017

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The reactions of nitramine, N-methyl nitramine, and N,N-dimethyl nitramine with anhydrous HF and the superacids HF/MF (M=As, Sb) were investigated at temperatures below -40 °C. In solution, exclusive O-protonation was observed by multinuclear NMR spectroscopy. Whereas no solid product could be isolated from the neat HF solutions even at -78 °C, in the HF/MF systems, protonated nitramine MF salts were isolated for the first time as moisture-sensitive solids that decompose at temperatures above -40 °C. In the solid state, depending on the counterion, O-protonated or N-protonated cations can be formed, in accord with theoretical calculations which show that the energy differences between O-protonation and N-protonation are very small. The salts [H N-NO H][AsF ], [H N-NO ][SbF ], [MeHNNO H][SbF ], and [Me NNO H][SbF ] were characterized by their X-ray crystal structures.

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Nitrogen: Inorganic ChemistryBased in part on the article Nitrogen: Inorganic Chemistry by Harry H. Sisler which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Hammerl¹,

Klapötke²

2005

Encyclopedia of Inorganic and Bioinorganic Chemistry

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The chemistry of nitrogen and its compounds with hydrogen, oxygen, and halogens is discussed in this article. The high stability of the nitrogen–nitrogen triple bond in dinitrogen in comparison with nitrogen–nitrogen single or double bonds makes polynitrogen compounds promising, highly energetic materials. Recently, several new polynitrogen species have been detected experimentally and salts of the polynitrogen cation N 5 + have been isolated in bulk. Salts of the azide anion N 3 − are already used as highly energetic materials. Binary compounds of nitrogen and hydrogen include ammonia, hydrazine, and several metastable species with nitrogen–nitrogen bonds. Ammonia, which is the starting material for all industrially produced nitrogen compounds, is probably the most important industrial chemical. Most of the ammonia produced is used as fertilizer, whereas hydrazine is used as an energetic material. The monomeric nitrogen oxides are among the most simple odd‐electron molecules and play an important role in the chemistry of the atmosphere. In combustion engines, huge amounts of nitric oxide are formed, which influence the ozone cycle both in the troposphere and in the stratosphere. Nitric oxide is a chemical messenger in biological systems and it helps to regulate a diverse array of physiological processes, such as neurotransmission, blood pressure and blood clot prevention. Oxoacids of nitrogen include hydroxylamine, nitrous acid, and nitric acid. Nitric acid is a major industrial chemical, which is primarily used for nitrate fertilizer production. Hydroxylamine is a starting material for the production of polyamide synthetics. Chlorine, bromine, and iodine halogen nitrogen compounds include halogensubstituted derivatives of ammonia, hydrazine, and diimine. They are unstable species that decompose to molecules in excited states. Nitrogen fluorides are thermodynamically more stable than the other nitrogen halides. Ternary compounds of nitrogen, oxygen, and halogens include nitrosyl‐ and nitrylhalides as well as the halogen nitrates. The stability of these compounds decreases from fluorine to iodine.

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Experimental and Theoretical Study on the Structure of Nitramide H₂NNO₂

Cited by 15 publications

References 12 publications

Photodissociation Mechanism of Nitramide: A CAS-SCF and MS-CASPT2 Study

Photodissociation Mechanism of Nitramide: A CAS-SCF and MS-CASPT2 Study

Protonation of Nitramines: Where Does the Proton Go?

Nitrogen: Inorganic ChemistryBased in part on the article Nitrogen: Inorganic Chemistry by Harry H. Sisler which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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Experimental and Theoretical Study on the Structure of Nitramide H2NNO2

Cited by 15 publications

References 12 publications

Photodissociation Mechanism of Nitramide: A CAS-SCF and MS-CASPT2 Study

Photodissociation Mechanism of Nitramide: A CAS-SCF and MS-CASPT2 Study

Protonation of Nitramines: Where Does the Proton Go?

Nitrogen: Inorganic ChemistryBased in part on the article Nitrogen: Inorganic Chemistry by Harry H. Sisler which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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Experimental and Theoretical Study on the Structure of Nitramide H₂NNO₂