Abstract
Integrated intensity measurements of the (100) and (101) x‐ray diffraction peaks of hexagonal selenium at pressures up to 52 kbar have permitted a determination of the atomic positions so that the bond distances and chain angle have been obtained at high pressure. The near‐neighbor bond distances along the Se chain remains essentially constant while the Se–Se–Se chain angle increases from 102.5° to 105.7°. The bond distance between the chains decreases by 9.7% at 52 kbar. The anomalous c‐axis expansion observed under pressure is thus explained as an enlargement of the chain angle pivoting about approximately fixed bond lengths along the chain.

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