Density function theory study of electronic, optical and thermodynamic properties of CaN₂, SrN₂ and BaN₂

Abstract

We put forward a first-principles density-functional theory about the impact of pressure on the structural and elastic properties of bulk CaN₂, SrN₂ and BaN₂. The ground state properties of three alkaline earth diazenides were obtained, and these were in good agreement with previous experimental and theoretical data. By using the quasi-harmonic Debye model, the thermodynamic properties including the debye temperature Θ _D, thermal expansion coefficient α, and grüneisen parameter γ are successfully obtained in the temperature range from 0 to 100 K and pressure range from 0 to 100 GPa, respectively. The optical properties including dielectric function ε(ϖ), absorption coefficient α(ϖ), reflectivity coefficient R(ϖ), and refractive index n(ϖ) are also calculated and analyzed.

Keywords

density functional theory / alkaline earth diazenides / electronic structure / thermodynamic properties / optical properties / pH

References

[1] Montoya J A, Hernandez C, Sanloup E, et al. OsN₂: Crystal Structure and Electronic Properties[J]. Appl. Phys. Lett., 2007, 90: 011909.

[2] Crowhurst J C, Goncharov B, Sadigh C L, et al. Synthesis and Characterization of the Nitrides of Platinum[J]. Science, 2006, 311: 275-1278.

[3] VON Appen J, Lumey R. Mysterious Platinum Nitride [J]. Angew Chem. Int. Ed., 2006, 45: 4365-4368.

[4] Auggrtmsnn G, Prots R. SrN and SrN₂: Diazenides by Synthesis under high N₂-Pressure[J]. Angew Chem. Int. Ed., 2001, 40: 547-549.

[5] Vajenine G V, Auffermann Y, Prots W, et al. Preparation, Crystal Structure, and Properties of Barium Pernitride, BaN₂[J]. Inorg. Chem., 2001, 40(19): 4866-4870.

[6] Michael W, Richard D. A First-principles Study on the Existence and Structures of the Lighter Alkaline-earth Pernitrides[J]. J. Comput. Chem., 2010, 31: 1613-1317.

[7] Vajenine G V, Auffermann G, Prots Y, et al. Preparation, Crystal Structure, and Properties of Barium Pernitride[J]. Inorg Chem., 2001, 40: 4866-4871.

[8] Auffermann G, Schmidt U, Bayer B, et al. Redox-Intercalation of Hydrogen and Nitrogen in Alkaline-Earth Subnitrides[J]. Anal. Bionan. Chem., 2002, 373: 880-886.

[9] Auffermann G, Kniep R, Bronger W Z. Reactive Gas Pressure Syntheses of Nitride-Diazenides and Hydridometalates[J]. Anorg. Allg. Chem., 2006, 632: 565-571.

[10] Gregoryanz E, Sanlout C, Somayazulu M, et al. Synthesis and Characterization of a Binary Noble Metal Nitride [J]. Nat. Mater., 2004, 3: 294.

[11] Von A J, Lumey M W, Dronskowski R. Schaltbare Hydrogele Durch Supramolekulare Vernetzung Adamantylhaltiger LCST-Copolymere Mit Cyclodextrin-Dimeren[J]. Angew. Chem., 2006, 118: 4468-4472.

[12] Crowhurst J C, Goncharow A F, Sadigh B, et al. Synthesis and Characterization of the Nitrides of Platinum[J]. Science, 2006, 311: 1275-1278.

[13] Young A F, Montoya J A, Sanloup C, et al. Interstitial Dinitrogen Mades PtN₂ an Insulating Hard Solid[J]. Phys. Rev. B, 2006, 73: 153102.

[14] Montoya J A, Hermandez A D, Sanloup C, et al. OsN: Crystal Structure and Electronic Properties[J]. Appl. Phys. Lett., 2007, 90: 011909.

[15] Chen Z W, Guo X J, Liu Z Y, et al. Crystal Structure and Physical Properties of OsN₂ and PtN₂ in the Marcastte Phase[J]. Phys. Rev. B, 2007, 75: 054103.

[16] Chen W, Jiang J Z. Stability, Elastic and Electronic Properties of Palladium Nitride[J]. Phys.: Condens. Matter., 2010, 22: 015404.

[17] Yu R, Zhan Q, De Jonghe L C. Crystal Structures of and Displacive Transitions IN OsN₂, IrN₂, RuN₂ and RhN₂[J]. Angew. Chem., 2007, 119: 1154-1158.

[18] Sebastain B S, Rainer F, Wolfgang S. Synthesis of Alkaline Earth Diazenides M(AE)N₂(M(AE)=Ca, Sr, Ba) by Controlled Thermal Decomposition of Zaides under High Pressure[J]. Inorg. Chem., 2012, 51: 2366.

[19] Milman V, Winkler B, White J A, et al. Electronic Structure, Properties, and Phase Stability of Inorganic Crystals: A Pseudopotential Plane-wave Study[J]. Int. J. Quantum. Chem., 2000, 77: 895-910.

[20] Perdew J P, Burke K, Ernzerhof M. Pressure and Temperature Dependence of the Lattice Dynamics of CuAlO₂ Investigated by Raman Scattering Experiments and ab initio Calculations[J]. Phys. Rev. Lett., 1996, 77: 3865.

[21] Monkhorst H J, Pack J D. Special Points for Brillouin-zone Integrations[J]. Phys. Rev. B., 1976, 13: 5188-5192.

[22] Vinet P, Rose J H, Ferrante J, et al. Universal Features of the Equation of State of Solids[J]. J. Phys.: Condens. Matter., 1989, 1: 1941-1964.

[23] Blanco M A, Francisco E, Luana V. GIBBS: Isothermal-Isobaric Thermodynamics of Solids from Energy Curves Using a Quasi-harmonic Debye Model[J]. Comput. Phys. Commun., 2004, 158: 57-72.

[24] Karki B B, Ackland G J, Crain J. Elastic Instabilities in Crystals from ab initio Stress-strain Relations[J]. J. Phys: Condens. Matter., 1997, 9: 8579.

[25] Voigt W, Der K L. New Calculus for Treatment of Optical Syustems[J]. Teubner, Leipzip., 1956, 46: 121-131.