Photon Echo Spectroscopy in Dye-Polymer Systems

S. Saikan
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Abstract

Recent experimental results on femtosecond accumulated photon echo in dye-polymer system are reviewed. This talk consists of two parts. The first half is concerned with the linear electron-phonon coupling in dye-polymer systems.1) The aim of this research is to clarify the parameter that is most important in significantly affecting the linear electron-phonon coupling in these materials,2) and to find the materials which have extremely weak linear electron-phonon coupling. In the theory of electron-phonon interaction, two parameters of Huang-Rhys factor and phonon frequency are important to characterize each material. Therefore, this research is closely related to the unsettled problem on the low frequency phonon mode in amorphous materials. It has been found that the peak frequency of the phonon sideband spectrum nearly coincides with the frequency of the boson peak that is observed in the Raman scattering spectrum of polymers,3) and that the Debye-Waller factor is larger for the polymers with higher boson peak frequency, such as hydrogen-bonded polymers. However, there seems to exist a maximum of the boson peak frequencyat around 40 cm-1 in organic polymers. This result explains the reason why it is difficult to develope the PHB memory material that works above the temperature of liquid nitrogen, so long as the dye-polymer systems are employed. As far as the dye-polymer system is concerned, the porphyrin substituted hemeproteins are, to the best of our knowledge, samples with very weak linear electron-phonon coupling.4) It is my opinion that the hydrophobic compartmentalization of the chromophores is the dominant mechanism that markedly reduces the electron-phonon coupling in the iron-free hemeproteins.
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染料-聚合物体系中的光子回波光谱
综述了近年来染料-聚合物体系飞秒累积光子回波的实验结果。这次演讲由两部分组成。前半部分是染料-聚合物体系中电子-声子的线性耦合。1)本研究的目的是澄清在这些材料中对电子-声子线性耦合有显著影响的最重要的参数,2)并找到线性电子-声子耦合极弱的材料。在电子-声子相互作用理论中,Huang-Rhys因子和声子频率是表征每种材料的重要参数。因此,本研究与非晶材料中低频声子模的未解决问题密切相关。研究发现,声子边带谱的峰值频率与聚合物拉曼散射谱中玻色子峰的频率几乎一致,并且对于高玻色子峰频率的聚合物,如氢键聚合物,Debye-Waller因子更大。然而,有机聚合物中似乎存在玻色子峰值频率在40 cm-1左右的最大值。这一结果解释了为什么只要采用染料-聚合物体系,就很难开发出工作在液氮温度以上的PHB记忆材料。就染料-聚合物体系而言,据我们所知,卟啉取代的血红蛋白是具有非常弱的线性电子-声子耦合的样品。4)我认为,在无铁血红蛋白中,发色团的疏水区隔化是显著降低电子-声子耦合的主要机制。
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