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 language | English |
|---|---|
| Pages (from-to) | 117-125 |
| Number of pages | 9 |
| Journal | Russian Journal of Physical Chemistry B |
| Volume | 8 |
| Issue number | 2 |
| DOIs | |
| Publication status | Published - 2014 |
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Keywords
- density functional theory
- Gibbs energy
- Helmholtz energy
- phonon thermal conductivity
- reactivity
- silver azide
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
Cite this
A study of the reactivity of silver azide based on calculations of the band properties within the framework of density functional theory. / Zhuravlev, Yu N.; Lisitsyn, V. M.
In: Russian Journal of Physical Chemistry B, Vol. 8, No. 2, 2014, p. 117-125.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - A study of the reactivity of silver azide based on calculations of the band properties within the framework of density functional theory
AU - Zhuravlev, Yu N.
AU - Lisitsyn, V. M.
PY - 2014
Y1 - 2014
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.
KW - density functional theory
KW - Gibbs energy
KW - Helmholtz energy
KW - phonon thermal conductivity
KW - reactivity
KW - silver azide
UR - http://www.scopus.com/inward/record.url?scp=84901022079&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84901022079&partnerID=8YFLogxK
U2 - 10.1134/S1990793114020109
DO - 10.1134/S1990793114020109
M3 - Article
VL - 8
SP - 117
EP - 125
JO - Russian Journal of Physical Chemistry B
JF - Russian Journal of Physical Chemistry B
SN - 1990-7931
IS - 2
ER -