Modulations in Intermetallic Families of Compounds
This thesis is based on a study of five distinct intermetallic systems with the aim of expanding the general knowledge of aperiodically modulated crystal structures. Families of compounds that contain a variety of superstructures together with incommensurately modulated structures have been investigated mainly by means of single crystal X-ray diffraction and higher dimensional structure models.A uniform (3+1)-dimensional structure for Bi-Se phases was developed with the composition as a single variable. The structure description is based on a cubic NaCl type structure with homoatomic layer stackings. It is shown by computational modelling that the formation energies of bismuth selenides with more than 40 at. % Bi are close to zero, a result that supports the idea of a continuous series of stackings corresponding to an ordered solid solution of Bi in Bi2Se3.The Nowotny chimney-ladder structures are described with a (3+1)-dimensional composite structure, valid for all such compounds regardless of the included elements, the composition or the valence electron concentration. A new member is added to this family by the ZrBi1.62 compound. The modulation is believed to arise as a secondary effect of the criteria of a fixed electron count.A symmetry analysis is presented for the RE1+?(MB)4 (RE = rare earth elements, M = iron metal elements) family of compounds and a uniform (3+1)-dimensional composite structure description has been developed. The modulation may be due to the presence of unusually short contacts between the RE channel atoms, giving rise to a rotational modulation of the (MB)4 tetraederstern chains.A (3+1)-dimensional incommensurate structure has been determined for the novel ?1 – CoZn compound. The structure displays a unique assembly of fused icosahedra and the modulation is induced by geometric strain.The structure of the K(PtSi)4 compound was re-determined. Despite a close kinship with the RE1+?(MB)4 compounds, this structure is not modulated.
Source Type:Doctoral Dissertation
Keywords:NATURAL SCIENCES; Chemistry; Inorganic chemistry; intermetallic; incommensurate structure; single crystal X-ray diffraction
Date of Publication:01/01/2004