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Title: First-principles high-pressure unreacted equation of state and heat of formation of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105)

Abstract

We report dispersion-corrected density functional theoretical calculations of the unreacted equation of state (EOS) of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105) under hydrostatic compression of up to 45 GPa. Convergence tests for k-points sampling in the Brillouin zone show that a 3 × 1 × 2 mesh is required to reproduce the X-ray crystal structure at ambient conditions, and we confirm our finding with a separate supercell calculation. Our high-pressure EOS yields a bulk modulus of 19.2 GPa, and indicates a tendency towards anisotropic compression along the b lattice vector due to molecular orientations within the lattice. We find that the electronic energy band gap decreases from a semiconductor type of 1.3 eV at 0 GPa to quasi-metallic type of 0.6 eV at 45 GPa. The extensive intermolecular hydrogen bonds involving the oxide (–NO) and dioxide (–NO{sub 2}) interactions with the amine (–NH{sub 2}) group showed enhanced interactions with increasing pressure that should be discernible in the mid IR spectral region. We do not find evidence for structural phase transitions or chemically induced transformations within the pressure range of our study. The gas phase heat of formation is calculated at the G4 level of theory to be 22.48 kcal/mol, while we obtainmore » 25.92 kcal/mol using the ccCA-PS3 method. Density functional theory calculations of the crystal and the gas phases provided an estimate for the heat of sublimation of 32.4 kcal/mol. We thus determine the room-temperature solid heat of formation of LLM-105 to be −9.9 or −6.5 kcal/mol based on the G4 or ccCA-PS3 methods, respectively.« less

Authors:
; ;  [1]
  1. Lawrence Livermore National Laboratory, Energetic Materials Center, Livermore, California 94551 (United States)
Publication Date:
OSTI Identifier:
22420036
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 6; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMINES; ANISOTROPY; BRILLOUIN ZONES; CRYSTAL STRUCTURE; CRYSTALS; DENSITY FUNCTIONAL METHOD; DISPERSIONS; EQUATIONS OF STATE; EV RANGE; FORMATION HEAT; INTERACTIONS; NITRIC OXIDE; NITROGEN DIOXIDE; PHASE TRANSFORMATIONS; SEMICONDUCTOR MATERIALS; SOLIDS; SUBLIMATION HEAT; X RADIATION

Citation Formats

Manaa, M. Riad, E-mail: manaa1@llnl.gov, Kuo, I-Feng W., and Fried, Laurence E. First-principles high-pressure unreacted equation of state and heat of formation of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105). United States: N. p., 2014. Web. doi:10.1063/1.4891933.
Manaa, M. Riad, E-mail: manaa1@llnl.gov, Kuo, I-Feng W., & Fried, Laurence E. First-principles high-pressure unreacted equation of state and heat of formation of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105). United States. doi:10.1063/1.4891933.
Manaa, M. Riad, E-mail: manaa1@llnl.gov, Kuo, I-Feng W., and Fried, Laurence E. Thu . "First-principles high-pressure unreacted equation of state and heat of formation of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105)". United States. doi:10.1063/1.4891933.
@article{osti_22420036,
title = {First-principles high-pressure unreacted equation of state and heat of formation of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105)},
author = {Manaa, M. Riad, E-mail: manaa1@llnl.gov and Kuo, I-Feng W. and Fried, Laurence E.},
abstractNote = {We report dispersion-corrected density functional theoretical calculations of the unreacted equation of state (EOS) of crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105) under hydrostatic compression of up to 45 GPa. Convergence tests for k-points sampling in the Brillouin zone show that a 3 × 1 × 2 mesh is required to reproduce the X-ray crystal structure at ambient conditions, and we confirm our finding with a separate supercell calculation. Our high-pressure EOS yields a bulk modulus of 19.2 GPa, and indicates a tendency towards anisotropic compression along the b lattice vector due to molecular orientations within the lattice. We find that the electronic energy band gap decreases from a semiconductor type of 1.3 eV at 0 GPa to quasi-metallic type of 0.6 eV at 45 GPa. The extensive intermolecular hydrogen bonds involving the oxide (–NO) and dioxide (–NO{sub 2}) interactions with the amine (–NH{sub 2}) group showed enhanced interactions with increasing pressure that should be discernible in the mid IR spectral region. We do not find evidence for structural phase transitions or chemically induced transformations within the pressure range of our study. The gas phase heat of formation is calculated at the G4 level of theory to be 22.48 kcal/mol, while we obtain 25.92 kcal/mol using the ccCA-PS3 method. Density functional theory calculations of the crystal and the gas phases provided an estimate for the heat of sublimation of 32.4 kcal/mol. We thus determine the room-temperature solid heat of formation of LLM-105 to be −9.9 or −6.5 kcal/mol based on the G4 or ccCA-PS3 methods, respectively.},
doi = {10.1063/1.4891933},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 6,
volume = 141,
place = {United States},
year = {2014},
month = {8}
}