Abstract
The Bi3+ion is characterized by the electronic configuration [Xe]4f145d106s2, and its 6s2lone pair plays an important role in the environment of the ion. A program of localization of the lone pair was successively applied to several bismuth oxides. Different Bi environments were then evidenced and a comparison between simple Bi oxides and more complex phases (modulated and collapsed phases in the family of the so-called Bi-2212 oxides or related compounds) was carried out. All these environments are characterized by Bi–Lpdistances ranging from 0.5 to 1 Å and O–Lpdistances above 2.4 Å. They can always be described as a more or less important distortion of an ideal BiO3Lptetrahedron. The possible role of this lone pair in the accommodation of the modulation in some phases is outlined.
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