Density functional theory investigation of sodium azide at high pressure

• Published in: Journal of physics. Conference series 2014-01, Vol.500 (16), p.162005-6
• Main Authors: Steele, B A, Landerville, A C, Oleynik, I I
• Format: Article
• Language: English
• Subjects: Bending; Compressing; Density functional theory; Distortion; Equations of state; First principles; Infrared spectra; Lattice vibration; Mathematical analysis; Phase transformations; Phase transitions; Physics; Raman spectra; Raman spectroscopy; Sodium; Sodium azides; Spectrum analysis
• ISSN: 1742-6596; 1742-6588; 1742-6596
• DOI: 10.1088/1742-6596/500/16/162005

High pressure experiments utilizing Raman spectroscopy indicate that the a phase of sodium azide undergoes a polymeric phase transition at high pressure. In this work, the structural and vibrational properties, including the first order Raman and infrared spectra, of the a phase of sodium azide are calculated using first-principles density functional theory up to 92 GPa. The equation of state of α NaN3 is obtained within the quasi-harmonic approximation at various temperatures. Each Raman-active mode blue shifts under compression whereas the doubly degenerate IR-active azide bending mode red-shifts under compression. However, at 70 GPa, the intensity of the Bu IR-active bending mode decreases substantially, and a new distorted azide bending lattice mode appears in the IR spectrum. In contrast to the bending mode, this new mode blue-shifts under compression. No new modes appear in the Raman spectra at high pressure, indicating that the changes in the Raman spectrum seen in experiment at high pressure are signs of new high nitrogen content structures, but not due to sodium azide.