The high-pressure phases of group-VI elements sulfur and selenium in their spiral chain and ring structures are examined by in situ Raman and x-ray diffraction techniques combined with first principles electronic structure calculations. The S-II, S-III, Se-I, and Se-VII having spiral chain structures and S-VI with a molecular six-member ring structure are studied in a wide P-T range. The square spiral chain structure of S-III and Se-VII is characterized by seven Raman modes that harden with increasing pressure. The calculations reproduce the observed frequencies and allow the authors to make the mode assignment. The p-S and hplt phases of sulfur reported by previous Raman studies are identified as S-II and S-III with the triangular and square spiral chain structures, respectively. The phase relations obtained by the x-ray and Raman measurements show that the high-pressure high-temperature phases of sulfur, observed by x-ray, can be induced by laser illumination at room temperature. (c) 2007 American Institute of Physics.
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