Pressure and temperature dependence of Raman scattering and optical absorption in crystalline S₄N₄

Raman scattering and optical absorption in crystalline S₄N₄ have been measured both as a function of pressure at 295 K and low temperatures. Polarized single crystal Raman data were also obtained as an aid in the assignment of the Raman active phonons. The pressure coefficients of the Raman active external and S-S stretching modes show a discontinuity near 7 kbar indicative of a second order phase change. The optical absorption edge at about 2.5 eV of a sublimed film of S₄N₄ shows red shifts of 1.3 × 10^-5 eV bar^-1 and 6.3 × 10^-4 eV K^-1 with pressure and temperature respectively. In the light of these results, the electronic, vibrational and structural properties of the crystal are discussed.