We report on a detailed, temperature-dependent, off-resonant Raman scattering study of glassy and supercooled selenium. Raman spectra in the frequency regime of the first-order scattering (5-450 cm(-1)) have been recorded over a wide temperature range, i.e., 143-353 K. To facilitate the analysis, the spectra have intuitively been divided in three spectral regions. The analysis of the high frequency region (bond-stretching vibrational modes) yielded information on the rings-chains equilibrium. In particular, the polymer content was found to amount to more than 85% around the glass transition temperature, exhibiting a weak temperature dependence, which extrapolates nicely to the high-temperature dissolution data. The intermediate frequency range (representative of the medium-range structural order) was treated together with the low frequency regime (where low-energy excitations, i.e., the quasielastic line and the Boson peak are the dominant contributions) owing to their strong overlap. The study of the bond-bending regime revealed information which made it possible to clarify the role of ringlike and chainlike fragments incorporated in polymeric molecules. The temperature evolution of the Boson peak and the frequency dependence of the Raman coupling coefficient Comega were also determined. An attempt to decompose the partial contribution of the pure Boson peak to Comega revealed valuable information concerning the limiting (omega-->0) behavior of the coupling coefficient.
Copyright 2004 American Institute of Physics