Sulfur allotropes Raman spectra

Fig. 29 Raman spectrum of p-S at high pressure and room temperature [109]. The wavenumbers indicated are given for the actual pressure. No signals of other allotropes have been detected. The line at 48 cm (ca. 25 cm atp 0 GPa) may arise from lattice vibrations, while the other lines resemble the typical pattern of internal vibrations of sulfur molecules...

Since the vibrational spectra of sulfur allotropes are characteristic for their molecular and crystalline structure, vibrational spectroscopy has become a valuable tool in structural studies besides X-ray diffraction techniques. In particular, Raman spectroscopy on sulfur samples at high pressures is much easier to perform than IR spectroscopical studies due to technical demands (e.g., throughput of the IR beam, spectral range in the far-infrared). On the other hand, application of laser radiation for exciting the Raman spectrum may cause photo-induced structural changes. High-pressure phase transitions and structures of elemental sulfur at high pressures were already discussed in [1]. 

At least five high-pressure allotropes of sulfur have been observed by Raman spectroscopy up to about 40 GPa the spectra of which differ significantly from those of a-Sg at high pressures photo-induced amorphous sulfur (a-S) [57, 58, 109, 119, 184-186], photo-induced sulfur (p-S) [57, 58, 109, 119, 184, 186-191], rhombohedral Se [58, 109, 137, 184, 186, 188, 191], high-pressure low-temperature sulfur (hplt-S) [137, 184, 192], and polymeric sulfur (S ) [58, 109, 119, 193]. The Raman spectra of two of these d-lotropes, a-S and S, were discussed in the preceding section. The Raman spectra of p-S and hplt-S have only been reported for samples at high-pressure conditions. The structure of both allotropes are imknown. The Raman spectrum of Se at STP conditions is discussed below. 

An illustrative example of the influence of symmetry on the number of vibrations is provided by the homologous series of cyclic sulfur allotropes S (n = 6-12). The IR absorptions for these ring systems are weak owing to the low polarity of S-S bonds. However, sulfur is a good Raman scatterer because S-S bonds are readily polarised. The various sulfur allotropes have different symmetries in addition to a different number of sulfur atoms and, consequently, each allotrope exhibits a characteristic Raman spectrum (Figure 3.8). ... 

When Sio was prepared from Se according to several slightly different procedures (see above) the formation of a new sulfur allotrope was observed several times. This allotrope forms intense orange-yellow, opaque, hexagonal plate-like crystals [34, 35]. An X-ray study on single crystals of this allotrope proved the assumption of a molecular addition compound Se-Sm as had been suggested before by evaluation of the Raman spectrum [34, 35],... 

---