Pressure Raman effects and internal stress in network glasses

Raman scattering from binary GexSe1−x glasses under hydrostatic pressure shows onset of a steady increase in the frequency of modes of corner-sharing GeSe4 tetrahedral units when the external pressure P exceeds a threshold value Pc. The threshold pressure Pcsxd decreases with x in the 0.15,x,0.20 range, nearly vanishes in the 0.20,x,0.25 range, and then increases in the 0.25,x,1/3 range. These Pcsxd trends closely track those in the nonreversing enthalpy, DHnrsxd, near glass transitions sTgsd, and in particular, both DHnrsxd and Pcsxd vanish in the reversibility window s0.20,x,0.25d. It is suggested that Pc provides a measure of stress at the Raman-active units, and its vanishing in the reversibility window suggests that these units are part of an isostatically rigid backbone. Isostaticity also accounts for the nonaging behavior of glasses observed in the reversibility window.