An extremely large displacement of the indium site in In-S octahedra in LnOInS (Ln = La, Ce, and Pr) was found in synchrotron X-ray diffraction. LaOInS with off-center indium in In-S octahedra exhibited a wider optical band gap than CeOInS and PrOInS with on-center indium. Therefore, the electronic structure of LnOInS is governed by the indium site with an extremely large displacement. All LnOInS produced H gas under visible light irradiation in the presence of sacrificial electron donors.
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