Polysilane electronic structure

The next-nearest-neighbor-orbital resonance integrals, /JI3, also remain unaffected by the pure twisting motion. We conclude that a pure twisting motion can therefore represent at best only a relatively small perturbation of the electronic structure of the polysilane chain, suitable for treatment by first-order perturbation theory. The perturbation is represented by changes in the resonance integrals between more distant hybrid orbitals, among which / 14 clearly is the most important. 

The conformational mobility of a chromophoric main-chain polymer is often connected to its electronic structure. Therefore, changes in the UV-visible absorption spectra and/or chiroptical properties are spectroscopically observable as thermo-, solvato-, piezo-, or electrochromisms. It is widely reported that o-conjugating polysilanes exhibit these phenomena remarkably clearly.34 However, their structural origins were controversial until recently, since limited information was available on the correlation between the conformational properties of the main chain, electronic state, and (chir)optical characteristics. In 1996, we reported that in various polysilanes in tetrahydrofuran (THF) at 30°C, the main-chain peak intensity per silicon repeat unit, e (Si repeat unit)-1 dm3 cm-1, increases exponentially as the viscosity index, a, increases.41 Although conventional viscometric measurements often requires a wide range of low-dispersity molecular-weight polymer samples, a size exclusion chromatography (SEC) machine equipped with a viscometric detector can afford... 

Dr. Keisuke Ebata, and Dr. Kazuaki Furukawa are thanked for valuable discussions on the electronic structure and optoelectronic properties of polysilanes at NTT. Prof. Nobuo Matsumoto (Shonan Institute of Technology), and Drs. Masao Morita, Kei-ichi Torimitsu, and Hideaki Takayanagi are acknowledged for encouragement and generous support at NTT during the course of this study. 

Michl, J. West, R. Electronic Structure and Spectroscopy of Polysilanes. In Silicon-based Polymers The Science and Technology of their Synthesis and Application-, Jones, R. G., Ando, W., Chojnowski, J., Eds. Kluwer Dordrecht, 2000 pp 499-529. 

The electronic structures of polysilane radical ions have also been studied by pulse radiolysis of the liquid solution [35-40]. However, due to short lifetime of the radical ions, the measurement is limited to electronic absorption spectroscopy. 

The conformational mobility of a chromophoric main chain polymer is often connected to its electronic structure. Therefore, changes in the UV-visible absorption spectra and/or chiroptical properties are spectroscopically observable as thermo-, solvato-, piezo-, or/and electrochromisms. It is widely reported that a-conjugating polysilanes exhibit these phenomena remarkably clearly [54], However, their structural origins were controversial until recently, since limited information was available on the correlation between the conformational prop-... 

The conformational structures of polysilane main chains at the macro-and microscopic levels are controllable by suitable choice of the side chain structures. Similarly, it is also the side chain which controls the optoelectronic properties by effecting the optical band gap. In the case of phenyl-substituted polysilanes, electronic interaction between the delocalized Si chain cr-bonding orbitals and the it-orbitals of the aryl groups causes a dramatic modification of both the band gap and conformational properties [61,83]. These aryl-containing polysilanes may be potential candidates for applications in a molecular-based chiroptical switch and memory in the UV/visible region. On the other hand, the precise control of helical polymers is now a subject of great interest and importance, due to the tech-... 

Properties such as photoconduc.tivityl l t l and photoluminescence of silicon polymers have been reported because of their wider optical band gap compared with crystalline silicon. Theoretical investigations of silicon polymers have been also reported ll2l-[21] Xakeda, Matsumoto and Fukuchi calculated the electronic structure of polysilane chains using the semi-empirical approach called the Complete Neglect of Differential Overlaps (CNDO) Molecular-Orbital (MO) method They discussed the dependence of the size and... 

Crystalline and amorphous silicons, which are currently investigated in the field of solid-state physics, are still considered as unrelated to polysilanes and related macromolecules, which are studied in the field of organosilicon chemistry. A new idea proposed in this chapter is that these materials are related and can be understood in terms of the dimensional hierarchy of silicon-backbone materials. The electronic structures of one-dimensional polymers (polysilanes) are discussed. The effects of side groups and conformations were calculated theoretically and are discussed in the light of such experimental data as UV absorption, photoluminescence, and UV photospectroscopy (UPS) measurements. Finally, future directions in the development of silicon-based polymers are indicated on the basis of some novel efforts to extend silicon-based polymers to high-dimensional polymers, one-dimensional superlattices, and metallic polymers with alternating double bonds. 

Figure 7. Schematic view of polysilane band structure. The abbreviations and symbols are defined as follows me, effective mass of electrons mh effective mass of holes lumi., luminescence abs., absorption T, k = 0 point and k,...

Side-chain substitutions and conformation variations perturb the detailed electronic structures of polysilanes. Substitution by larger alkyl side chains decreases the band gap slightly because of the electron-donating... 

Fluorescence spectroscopy in combination with circular dichroism (CD), optical rotatory dispersion. X-ray crystallography, UV and NMR spectroscopy of the main chain is a powerful probe for identifying helical conformation, uniformity, and rigidity in polymers. In recent years, these techniques have been applied extensively to investigate the structures of polysilanes in both the solid state and in solution and it is now clear that after electronic structure main chain helicity is the principal determinant of the properties of polysilanes. In... 

Michl J, West R (2000). Electronic structure and spectroscopy of polysilanes. In Jones RG, Ando W, Chojnowski J (eds) Silicon containing polymers. Kluwer Academic, Dordrecht, pp 499-529... 

Abstract The linear and nonlinear optical properties of polysilanes, and in particular poly(di-n-hexylsilane), have been investigate by vacuum UV spectroscopy and by two-photon induced processes. The electronic structure of the polymer inferred from these measurements is consistent with models which view the polymer as a one-dimensional semiconductor quantum wire. The exciton related optical nonlinearities are also large enough to allow polysUanes to be considered for various nonlinear switching applications. 

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