Terahertz time-domain spectroscopy and low-frequency Raman scattering were performed on the natural polymer starch to investigate the boson peak (BP) dynamics. In the infrared spectrum, the BP was observed at 0.99THz at the lowest temperature. Compared to the result from a previous study for vitreous glucose, both the frequency of the BP and absorption coefficient show lower values than those of the vitreous glucose. These behaviors originate from the longer correlation length of the medium-range order and lower concentration of hydroxyl groups in the starch. In the Raman spectrum, the BP was observed at 1.1THz at room temperature, although the BP was not observed around room temperature due to the excess wing of the fast relaxation modes in the infrared spectrum. The temperature dependence of ε″(ν) during the heating process and cooling process shows a hysteresis below 230K. During the heating process, kinks were observed at 140K and 230K. These kinks are attributed to the β-relaxation and the β-relaxation, respectively.
Disordered systems exhibit universal excitation, referred to as the boson peak, in the terahertz region. Meanwhile, the so-called fracton is expected to appear in the nanoscale region owing to the self-similar structure of monomers in polymeric glasses. We demonstrate that such excitations can be detected using terahertz spectroscopy. For the interaction between terahertz light and the vibrational density of states of the fractal structure, we formulate an infrared light-vibration coupling coefficient for the fracton region. Accordingly, we show that information concerning fractal and fracton dimensions appears in the exponent of the absorption coefficient. Finally, using terahertz time-domain spectroscopy and low-frequency Raman scattering, we experimentally observe these universal excitations in a protein lysozyme system that has an intrinsically disordered and self-similar nature in a single supramolecule. These findings are applicable to disordered and polymeric glasses in general and will be key to understanding universal dynamics of disordered systems by terahertz light.
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