Dense nitrogen-rich energetic materials: A study of 5,5′-bis(1<i>H</i>-tetrazolyl)amine

Laniel, Dominique; Sebastiao, Elena; Cook, Cyril; Murugesu, Muralee; Hu, Amanda; Zhang, Fan; Desgreniers, Serge

doi:10.1063/1.4870830

Cited by 9 publications

(9 citation statements)

References 25 publications

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“…Electronic mail: erb@lamar.colostate.edu the ideal candidates for next generation energetic materials. 5,10 The decomposition of these compounds results predominantly in generation of N 2 , which renders them friendly to the environment. 7 Such decompositions are accompanied by an enormous energy release due to the wide difference in the average bond energies of N-N (160 kJ/mol) and N= =N (418 kJ/mol), compared to that of N≡ ≡N (954 kJ/mol).…”

Section: Introductionmentioning

confidence: 99%

“…7 Such decompositions are accompanied by an enormous energy release due to the wide difference in the average bond energies of N-N (160 kJ/mol) and N= =N (418 kJ/mol), compared to that of N≡ ≡N (954 kJ/mol). 5,10 Nitrogen rich compounds based on tetrazole rings are used as energetic materials. These species have intra-/inter-molecular N-H • • • H hydrogen bonds and π-π stacking interactions between adjacent tetrazole rings in arrays for high density: they occupy ideal middle ground for thermal and physical stability versus performance (stored energy density).…”

Section: Introductionmentioning

confidence: 99%

“…The two tetrazole rings can rotate with respect to the plane of the -C-NH-C-amine group by 180 • . 10 Neutral BTA possesses high thermal and mechanical stability with a high nitrogen content (82.34 w%). 14,15 It is considered to be an interesting nitrogen-rich framework for energetic salts because of its multi-proton donor sites with three reversible types of protonated and deprotonated analogues: BTA, BTA − , and BTA 2− .…”

Section: Introductionmentioning

confidence: 99%

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Initial mechanisms for the unimolecular decomposition of electronically excited nitrogen-rich energetic materials with tetrazole rings: 1-DTE, 5-DTE, BTA, and BTH

Yuan

Bernstein

2016

The Journal of Chemical Physics

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Unimolecular decomposition of nitrogen-rich energetic molecules 1,2-bis(1H-tetrazol-1-yl)ethane (1-DTE), 1,2-bis(1H-tetrazol-5-yl)ethane (5-DET), N,N-bis(1H-tetrazol-5-yl)amine (BTA), and 5,5'-bis(tetrazolyl)hydrazine (BTH) has been explored via 283 nm two photon laser excitation. The maximum absorption wavelength in the UV-vis spectra of all four materials is around 186-222 nm. The N2 molecule, with a cold rotational temperature (<30 K), is observed as an initial decomposition product from the four molecules, subsequent to UV excitation. Initial decomposition mechanisms for these four electronically excited isolated molecules are explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) level illustrate that conical intersections play an essential role in the decomposition mechanism. The tetrazole ring opens on the S1 excited state and through conical intersections (S1/S0)CI, N2 product is formed on the ground state potential energy surface without rotational excitation. The tetrazole rings of all four energetic molecules open at the N1-N2 ring bond with the lowest energy barrier: the C-N bond opening has higher energy barrier than that for any of the N-N ring bonds. Therefore, the tetrazole rings open at their N-N bonds to release N2. The vibrational temperatures of N2 product from all four energetic materials are hot based on theoretical calculations. The different groups (CH2-CH2, NH-NH, and NH) joining the tetrazole rings can cause apparent differences in explosive behavior of 1-DTE, 5-DTE, BTA, and BTH. Conical intersections, non-Born-Oppenheimer interactions, and dynamics are the key features for excited electronic state chemistry of organic molecules, in general, and energetic molecules, in particular.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Initial mechanisms for the unimolecular decomposition of electronically excited nitrogen-rich energetic materials with tetrazole rings: 1-DTE, 5-DTE, BTA, and BTH

Yuan

Bernstein

2016

The Journal of Chemical Physics

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“…However, the pressure dependence of the a - and b -axes are not well represented with a linear fit, instead an empirical equation fits the curvature at low pressures much better, giving the compressibility range of Ka = 34–19 TPa−1 and Kb = 40–20 TPa−1 (Figure S1). Anisotropic changes in lattice parameters are very common in molecular materials due to the packing motifs and differing strengths of molecular interactions along different directions in the unit cell [14,23,24].…”

Section: Resultsmentioning

confidence: 99%

Packing Rearrangements in 4-Hydroxycyanobenzene Under Pressure

Collings

Hanfland

2019

Molecules

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4-hydroxycyanobenzene (4HCB) is a dipolar molecule formed of an aromatic substituted benzene ring with the CN and OH functional groups at the 1 and 4 positions. In the crystalline state, it forms spiral chains via hydrogen bonding, which pack together through π − π interactions. The direct stacking of benzene rings down the a- and b-axes and its π − π interactions throughout the structure gives rise to its semiconductor properties. Here, high-pressure studies are conducted on 4HCB in order to investigate how the packing and intermolecular interactions, related to its semiconductor properties, are affected. High-pressure single-crystal X-ray diffraction was performed with helium and neon as the pressure-transmitting mediums up to 26 and 15 GPa, respectively. The pressure-dependent behaviour of 4HCB in He was dominated by the insertion of He into the structure after 2.4 GPa, giving rise to two phase transitions, and alterations in the π − π interactions above 4 GPa. 4HCB compressed in Ne displayed two phase transitions associated with changes in the orientation of the 4HCB molecules, giving rise to twice as many face-to-face packing of the benzene rings down the b-axis, which could allow for greater charge mobility. In the He loading, the hydrogen bonding interactions steadily decrease without any large deviations, while in the Ne loading, the change in 4HCB orientation causes an increase in the hydrogen bonding interaction distance. Our study highlights how the molecular packing and π − π interactions evolve with pressure as well as with He insertion.

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“…Pathways to a stable single-bonded polymeric network at room conditions need to be studied. In that context, nitrogenrich molecular precursors, particularly ionic azides [5][6][7][8] and carbon nitrides, 3,[9][10][11][12][13] have been extensively investigated under extreme conditions. Such compounds could form a metastable network comprising single-bonded nitrogen atoms which would have mainly N 2 as a decomposition product.…”

Section: Introductionmentioning

confidence: 99%

High pressure study of a highly energetic nitrogen-rich carbon nitride, cyanuric triazide

Laniel

Downie

Smith

et al. 2014

The Journal of Chemical Physics

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Cyanuric triazide (CTA), a nitrogen-rich energetic material, was compressed in a diamond anvil cell up to 63.2 GPa. Samples were characterized by x-ray diffraction, Raman, and infrared spectroscopy. A phase transition occurring between 29.8 and 30.7 GPa was found by all three techniques. The bulk modulus and its pressure derivative of the low pressure phase were determined by fitting the 300 K isothermal compression data to the Birch-Murnaghan equation of state. Due to the strong photosensitivity of CTA, synchrotron generated x-rays and visible laser radiation both lead to the progressive conversion of CTA into a two dimensional amorphous C=N network, starting from 9.2 GPa. As a result of the conversion, increasingly weak and broad x-ray diffraction lines were recorded from crystalline CTA as a function of pressure. Hence, a definite structure could not be obtained for the high pressure phase of CTA. Results from infrared spectroscopy carried out to 40.5 GPa suggest the high pressure formation of a lattice built of tri-tetrazole molecular units. The decompression study showed stability of the high pressure phase down to 13.9 GPa. Finally, two CTA samples, one loaded with neon and the other with nitrogen, used as pressure transmitting media, were laser-heated to approximately 1100 K and 1500 K while compressed at 37.7 GPa and 42.0 GPa, respectively. In both cases CTA decomposed resulting in amorphous compounds, as recovered at ambient conditions.

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Dense nitrogen-rich energetic materials: A study of 5,5′-bis(1H-tetrazolyl)amine

Cited by 9 publications

References 25 publications

Initial mechanisms for the unimolecular decomposition of electronically excited nitrogen-rich energetic materials with tetrazole rings: 1-DTE, 5-DTE, BTA, and BTH

Initial mechanisms for the unimolecular decomposition of electronically excited nitrogen-rich energetic materials with tetrazole rings: 1-DTE, 5-DTE, BTA, and BTH

Packing Rearrangements in 4-Hydroxycyanobenzene Under Pressure

High pressure study of a highly energetic nitrogen-rich carbon nitride, cyanuric triazide

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