| 【文章摘要】 The structural and elastic properties of the recently-discovered wⅡ- and δ-Si_3N_4 are investigated through the plane-wave pseudo-potential method within ultrasoft pseudopotentials.The elastic constants show that wⅡ- and δ-Si_3N_4 are mechanically stable in the pressure ranges of 0-50 GPa and 40-50 GPa,respectively.The α→wⅡ phase transition can be observed at 18.6 GPa and 300 K.The β→δ phase transformation occurs at pressures of 29.6,32.1,35.9,39.6,41.8,and 44.1 GPa when the temperatures are100,200,300,400,500,and 600 K,respectively.The results show that the interactions among the N-2s,Si-3s,3p bands(lower valence band) and the Si-3p,N-2p bands(upper valence band) play an important role in the stabilities of the wⅡ and S phases.Moreover,several thermodynamic parameters(thermal expansion,free energy,bulk modulus and heat capacity) of δ-Si_3N_4 are also obtained.Some interesting features are found in these properties.δ-Si_3N_4 is predicted to be a negative thermal expansion material.The adiabatic bulk modulus decreases with applied pressure,but a majority of materials show the opposite trend.Further experimental investigations with higher precisions may be required to determine the fundamental properties of wⅡ- andδ-Si_3N_4. |