TITLE

Computational studies on the infrared vibrational spectra, thermodynamic properties, detonation properties, and pyrolysis mechanism of octanitrocubane

AUTHOR(S)
Zhang, Ji; Xiao, Heming
PUB. DATE
June 2002
SOURCE
Journal of Chemical Physics;6/22/2002, Vol. 116 Issue 24, p10674
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
The molecular geometries, infrared vibrational spectra, and thermodynamic properties of octanitrocubane (ONC) are calculated using the density functional theory (DFT) method at the B3LYP/6-31G[sup *] level. The IR frequency scaling factor 0.9501 suitable for polynitrocubanes is obtained at the B3LYP/6-31G[sup *] level, and the calculated IR frequencies of ONC are scaled. The accurate heat of formation 726.47 kJ/mol of ONC in gas phase is obtained via designed isodesmic reaction in which the cubane cage skeleton has been kept. The sublimation enthalpy, density, and heat of formation for ONC crystal are also calculated, and they are 220.63 kJ/mol, 2.189 g/cm³, and 505.84 kJ/mol, respectively. In addition, the estimated detonation velocity and detonation pressure of ONC are 10.26 mm/ms and 520.86 kbar, respectively. Finally, the pyrolysis mechanism of ONC is studied using various theoretical methods, i.e., MP2, DFT, and selected MINDO/3 semiempirical MO, based on the unrestricted Hartree-Fock model. The calculated results show that the pyrolysis initiation reaction of ONC, i.e., rate-controlling step, is to form a diradical by the single C-C bond breaking in the cube. The second C-C bond breaking is easily followed to form a nitrocyclooctatetraene. The calculated activation energy for the pyrolysis initiation reaction of ONC, obtained from B3LYP/6-31G[sup *] method, is 155.30 kJ/mol, which this rather large activation energy indicates that ONC is a new type of energetic material with less sensitivity and better thermal stability, and has highly exploitable values.
ACCESSION #
6789917

 

Related Articles

  • Turbostratic carbon nitride prepared by pyrolysis of melamine. Zhao, Y.; Yu, D.; Zhou, H.; Tian, Y.; Yanagisawa, O. // Journal of Materials Science;May2005, Vol. 40 Issue 9/10, p2645 

    In this article the authors present a method to prepare turbostratic carbon nitride by pyrolysis of melamine. Due to the great thermodynamic stability of nitrogen, however, the ideal structural transition from precursor to crystalline carbon nitride is difficult to realize. In most cases, only...

  • Thermodynamic Analysis of the High Temperature Processes in the System Si-C-H-Cl. Lilov, Stanislav // AIP Conference Proceedings;2007, Vol. 899 Issue 1, p621 

    In the present work a thermodynamic analysis of the interaction processes in the Si-C-H-Cl system in the temperature interval 1000–3000 K is carried out. The optimal conditions giving the maximum yield of the silicon carbide by pyrolysis of mixture of volatile compounds of carbon and...

  • Investigation of the gas-phase B–X electronic spectra of CH–Ar by laser-induced fluorescence. Lemire, G. W.; McQuaid, M. J.; Kotlar, A. J.; Sausa, R. C. // Journal of Chemical Physics;7/1/1993, Vol. 99 Issue 1, p91 

    Gas-phase methyidyne–argon (CH–Ar) van der Waals complexes have been detected spectroscopically by laser-induced fluorescence (LIF) in the region of the CH B 2Σ-–X 2Πr (0,0) and (1,0) bands near 363.5 and 388.9 nm, respectively. They are formed by a supersonic free-jet...

  • Pyrolysis jet spectroscopy: The S1–S0 band system of formyl cyanide, HCOCN, and DCOCN. Clouthier, Dennis J.; Karolczak, J.; Rae, J.; Chan, W.-T.; Goddard, J. D.; Judge, R. H. // Journal of Chemical Physics;8/1/1992, Vol. 97 Issue 3, p1638 

    The A 1A‘–X 1A’ band systems of HCOCN and DCOCN have been studied in depth using the technique of pyrolysis jet spectroscopy. Ab initio predictions of molecular structures and vibrational frequencies for the ground and excited state were made, to assist in the assignment of...

  • Rate coefficients for rotationally inelastic collisions of CO with H[sub 2]. Mengel, Markus; De Lucia, Frank C.; Herbst, Eric // Canadian Journal of Physics;Feb2001, Vol. 79 Issue 2, p589 

    We have performed quantum-scattering calculations to determine inelastic rate coefficients of the astrophysically important collision system CO–H[sub 2] . We have used a modified version of the most recent potential-energy surface by Jankowski and Szalewicz (J. Chem. Phys. 108, 3554...

  • C+(2P)+H2(D2,HD)→CH+(CD+)+H(D). II. Statistical phase space theory. Ervin, Kent M.; Armentrout, P. B. // Journal of Chemical Physics;6/15/1986, Vol. 84 Issue 12, p6750 

    Statistical phase space theory is applied to the reactions of carbon(1+)ions with isotopic molecular hydrogen (H2, D2, and HD) to form methyliumylidene (CH+ and CD+). Reaction cross sections and isotope effects as a function of kinetic energy are compared to recent experimental results. The...

  • Nematic ordering of 4-n-alkyl-4’-cyanobiphenyls studied by carbon-13 NMR with off-magic-angle spinning. Fung, B. M.; Afzal, Jalees; Foss, Tina L.; Chau, Mei-Hing // Journal of Chemical Physics;11/1/1986, Vol. 85 Issue 9, p4808 

    A method called RHODIUM (removal of homonuclear dipolar coupling and the use of off-magic-angle spinning) can be applied effectively to study the carbon-13 NMR of liquid crystals in natural abundance. In this method, the sample is spun rapidly (∼1 kHz) at an angle (θ) slightly less than...

  • The far infrared spectrum of C3O2. Vander Auwera, J.; Johns, J. W. C.; Polyansky, O. L. // Journal of Chemical Physics;8/15/1991, Vol. 95 Issue 4, p2299 

    The far infrared spectrum of carbon suboxide, 12C316O2, has been recorded at a resolution of 0.003 cm-1 in the region from 15 to 130 cm-1 with a Bomem interferometer. Altogether 18 bands involving the excitation of up to 8 quanta in the low frequency quasilinear bending mode ν7 were analyzed...

  • The properties of CO and K co-adsorbed on Ni(111), studied by thermal desorption and metastable quenching spectroscopy. Lee, Jiwha; Arias, Jose; Hanrahan, Ciaran P.; Martin, Richard M.; Metiu, Horia // Journal of Chemical Physics;1/1/1985, Vol. 82 Issue 1, p485 

    We use thermal desorption and metastable quenching spectroscopy to study the (CO+K)/Ni(111) system. We find that CO and K co-adsorption increases the binding energy (to the surface) of both molecules; that at coverages of more than one potassium atom per, roughly, eight nickel atoms the adsorbed...

Share

Read the Article

Courtesy of VIRGINIA BEACH PUBLIC LIBRARY AND SYSTEM

Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics