Anisotropy in the electronic structure of polysilanes investigated by synchrotron-radiation spectroscopy

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Abstract
Using highly oriented films of poly(dihexylsilane), polarized absorption spectra were measured by means of synchrotron radiation in the energy range of 2–10 eV for the trans-planar conformation of Si-backbone structures. The absorption bands polarized parallel or perpendicular to the polymer backbones were observed below 8 eV, which have been interpreted as the σ-electron-related transitions or associated exciton states on the basis of theoretical electronic band structures. Taking advantage of the thermally induced change of the backbone structure from the ordered trans-planar to the disordered gauche-containing form, the conformation dependence of the electronic structures in Si chains was also investigated, which clearly demonstrates a reduced degree of delocalization of σ-electron states upon the conformation change.