Comparison of the molecular structure of hexahydro-1,3,5-trinitro-s-triazine in the vapor, solution and solid phases

Karpowicz, Richard J.; Brill, T. B.

doi:10.1021/j150647a005

Cited by 131 publications

(176 citation statements)

References 4 publications

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“…The structure demonstrates that the amine lone pair can be comfortably accommodated in any reasonable position, which, in turn, suggests that axial-equatorial interconversions of the NO 2 groups by stereochemical action of the amine lone pair might be facile. RDX molecules in solution and in the gas phase appear to have essentially C3v symmetry (Karpowicz & Brill, 1983), which is consistent with dynamic time-averaged axial-equatorial NO 2 motion. The directional activity of the amine lone pair may be at least partly responsible for the variations in the N--N bond lengths.…”

Section: Introductionsupporting

confidence: 66%

Structure of the 1:1 complex between hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and tetrahydrothiophene 1,1-dioxide (sulfolane), C3H6N6O6.C4H8O2S

Haller¹,

Brill²,

Rheingold³

1984

Acta Crystallogr C

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Abstract. M r = 342.28, triclinic, P1, a = 6.238 (2), b=10.241(3), c=11.271(3)A, t~=100.65 (2), fl =100.50(3), 7=94.193(3) o, V=691.5(4)/~ 3, Z =2, D x=1.64gcm -3, MoKt~, 2=0.71073/k, /t= 2.66 cm -l, F(000) = 340, T= 298 K, R v = 0.040 for 1605 observed reflections. The RDX molecule contains all of the three possible orientations of the NO2 groups (axial, equatorial, and planar). The ring conformation is chair. The sulfolane molecule is regular and normal, but may be partly responsible for the rather unusual positioning of the NO 2 groups of the RDX molecule.

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Section: Introductionsupporting

confidence: 66%

Structure of the 1:1 complex between hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and tetrahydrothiophene 1,1-dioxide (sulfolane), C3H6N6O6.C4H8O2S

Haller¹,

Brill²,

Rheingold³

1984

Acta Crystallogr C

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“…33 The frequencies are in agreement with experimental data. 35 These results show that doubly degenerate Q-distortions contribute significantly to renormalization of the hardness. The RDX molecule has a twofold degenerate HOMO ͑E symmetry͒ with energy E HOMO ϭϪ8.32 eV.…”

Section: Calculations For the Rdx Moleculementioning

confidence: 84%

A model for mechanochemical transformations: Applications to molecular hardness, instabilities, and shock initiation of reaction

Luty

Ordon

Eckhardt

2002

The Journal of Chemical Physics

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A basic theoretical structure for mechanochemical transformations based on prior models for solid-state reactions and HOMO-LUMO ͑highest occupied molecular orbital-lowest unoccupied molecular orbital͒ gap closing produces the concept of distortion-induced molecular electronic degeneracy ͑DIMED͒ of the highest occupied and lowest unoccupied molecular orbitals of an energetic molecule. Both intermolecular and intramolecular charge transfer are involved. The resulting distortion-induced local instability, a mechanochemical effect, leads to chemical transformations and can be analyzed by renormalization of the molecular hardness through the molecular deformation energy. Linear combinations of normal modes are shown to be useful for description of the mechanically induced reaction path. Numerical calculations for the RDX ͑hexahydro-1,3,5-trinitro-1,3,5-triazine͒ molecule are used to construct a path for initiation of a reaction by shock. They show the breaking of a single N-N bond as the primary step. DIMED is shown to be a kind of ''inverse Jahn-Teller effect'' leading to the general conclusion that distortion-induced instabilities and mechanically induced reactions require some, but not necessarily complete, HOMO-LUMO gap closure. This indicates that large local strains due to defects or cracks will contribute to DIMED. The DIMED concept, because of its generality, has wide applicability in solid-state chemistry.

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“…5,9 A theoretical investigation of hydrostatic compression of ␣-RDX was also performed by Byrd and Rice 22 using density functional theory ͑DFT͒. Elastic properties of ␣-RDX have also been investigated by both experiment and theory.…”

Section: 5mentioning

confidence: 99%

Density functional theory calculations of anisotropic constitutive relationships in alpha-cyclotrimethylenetrinitramine

Conroy

Oleynik

Zybin

et al. 2008

Journal of Applied Physics

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Constitutive relationships in the crystalline energetic material ␣-cyclotrimethylenetrinitramine ͑␣-RDX͒ have been investigated using first-principles density functional theory. The equilibrium properties of ␣-RDX including unit cell parameters and bulk modulus, as well as the hydrostatic equation of state ͑EOS͒, have been obtained and compared with available experimental data. The isotropic EOS has been extended to include the anisotropic response of ␣-RDX by performing uniaxial compressions normal to several low-index planes, ͕100͖, ͕010͖, ͕001͖, ͕110͖, ͕101͖, ͕011͖, and ͕111͖, in the Pbca space group. The uniaxial-compression data exhibit a considerable anisotropy in the principal stresses, changes in energy, band gaps, and shear stresses, which might play a role in the anisotropic behavior of ␣-RDX under shock loading.

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Comparison of the molecular structure of hexahydro-1,3,5-trinitro-s-triazine in the vapor, solution and solid phases

Cited by 131 publications

References 4 publications

Structure of the 1:1 complex between hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and tetrahydrothiophene 1,1-dioxide (sulfolane), C3H6N6O6.C4H8O2S

Structure of the 1:1 complex between hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and tetrahydrothiophene 1,1-dioxide (sulfolane), C3H6N6O6.C4H8O2S

A model for mechanochemical transformations: Applications to molecular hardness, instabilities, and shock initiation of reaction

Density functional theory calculations of anisotropic constitutive relationships in alpha-cyclotrimethylenetrinitramine

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