A study of the reactivity of silver azide based on calculations of the band properties within the framework of density functional theory

Yu N. Zhuravlev, V. M. Lisitsyn

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2 Citations (Scopus)

Abstract

Density functional theory methods in the basis of localized orbitals are used to study structural, electronic, vibrational, and thermodynamic properties, as well as the reactivity of the orthorhombic, tetragonal, and monoclinic phases of silver azide. The effects of pressure and temperature are described using the Debye quasi-harmonic model. The reactivity of silver azide is analyzed in terms of the enthalpy and entropy factors and equilibrium constants. It is shown that, for the solid-phase decomposition, a decrease in the volume (increase in pressure) leads to a decrease in the enthalpy, whereas the entropy factor remains virtually unchanged. As a result, at a pressure of 11.6 GPa, the reaction of direct generation of holes becomes feasible and then, above 14.8 GPa, exothermic. The formation of small nuclei of silver dinitride-nitride AgNN2 metastable phase is considered as a possible mechanism of generation of reaction kernels.

Original languageEnglish
Pages (from-to)117-125
Number of pages9
JournalRussian Journal of Physical Chemistry B
Volume8
Issue number2
DOIs
Publication statusPublished - 2014

Fingerprint

Density functional theory
reactivity
silver
density functional theory
Enthalpy
Entropy
enthalpy
entropy
Metastable phases
Equilibrium constants
Silver
Nitrides
nitrides
solid phases
Thermodynamic properties
thermodynamic properties
Decomposition
harmonics
decomposition
orbitals

Keywords

  • density functional theory
  • Gibbs energy
  • Helmholtz energy
  • phonon thermal conductivity
  • reactivity
  • silver azide

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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abstract = "Density functional theory methods in the basis of localized orbitals are used to study structural, electronic, vibrational, and thermodynamic properties, as well as the reactivity of the orthorhombic, tetragonal, and monoclinic phases of silver azide. The effects of pressure and temperature are described using the Debye quasi-harmonic model. The reactivity of silver azide is analyzed in terms of the enthalpy and entropy factors and equilibrium constants. It is shown that, for the solid-phase decomposition, a decrease in the volume (increase in pressure) leads to a decrease in the enthalpy, whereas the entropy factor remains virtually unchanged. As a result, at a pressure of 11.6 GPa, the reaction of direct generation of holes becomes feasible and then, above 14.8 GPa, exothermic. The formation of small nuclei of silver dinitride-nitride AgNN2 metastable phase is considered as a possible mechanism of generation of reaction kernels.",
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AU - Zhuravlev, Yu N.

AU - Lisitsyn, V. M.

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N2 - Density functional theory methods in the basis of localized orbitals are used to study structural, electronic, vibrational, and thermodynamic properties, as well as the reactivity of the orthorhombic, tetragonal, and monoclinic phases of silver azide. The effects of pressure and temperature are described using the Debye quasi-harmonic model. The reactivity of silver azide is analyzed in terms of the enthalpy and entropy factors and equilibrium constants. It is shown that, for the solid-phase decomposition, a decrease in the volume (increase in pressure) leads to a decrease in the enthalpy, whereas the entropy factor remains virtually unchanged. As a result, at a pressure of 11.6 GPa, the reaction of direct generation of holes becomes feasible and then, above 14.8 GPa, exothermic. The formation of small nuclei of silver dinitride-nitride AgNN2 metastable phase is considered as a possible mechanism of generation of reaction kernels.

AB - Density functional theory methods in the basis of localized orbitals are used to study structural, electronic, vibrational, and thermodynamic properties, as well as the reactivity of the orthorhombic, tetragonal, and monoclinic phases of silver azide. The effects of pressure and temperature are described using the Debye quasi-harmonic model. The reactivity of silver azide is analyzed in terms of the enthalpy and entropy factors and equilibrium constants. It is shown that, for the solid-phase decomposition, a decrease in the volume (increase in pressure) leads to a decrease in the enthalpy, whereas the entropy factor remains virtually unchanged. As a result, at a pressure of 11.6 GPa, the reaction of direct generation of holes becomes feasible and then, above 14.8 GPa, exothermic. The formation of small nuclei of silver dinitride-nitride AgNN2 metastable phase is considered as a possible mechanism of generation of reaction kernels.

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