Journal
JOURNAL OF MOLECULAR STRUCTURE
Volume 1069, Issue -, Pages 152-156Publisher
ELSEVIER SCIENCE BV
DOI: 10.1016/j.molstruc.2014.02.058
Keywords
Terahertz spectroscopy; Two-dimensional correlation spectroscopy; Low-frequency vibrational mode; Poly(3-hydroxybutyrate)
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Funding
- KAKENHI [20750067, 22360011]
- Industry-Academia Collaborative R&D from Japan Science and Technology Agency, JST
- Grants-in-Aid for Scientific Research [20750067, 22360011] Funding Source: KAKEN
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In this study, the terahertz (THz) absorption spectra of poly(3-hydroxybutyrate) (PHB) were measured during isothermal crystallization at 90-120 degrees C. The temporal changes in the absorption spectra were analyzed using two-dimensional correlation spectroscopy (2DCOS). In the asynchronous plot, cross peaks were observed around 2.4 THz, suggesting that two vibrational modes overlap in the raw spectrum. By comparing this to the peak at 2.9 THz corresponding to the stretching mode of the helical structure of PHB and the assignment obtained using polarization spectroscopy, we concluded that the high-frequency band could be attributed to the vibration of the helical structure and the low-frequency band to the vibration between the helical structures. The exact frequencies of the overlapping vibrational bands and their assignments provide a new means to inspect the thermal behavior of the intermolecular vibrational modes. The large red-shift of the interhelix vibrational mode suggests a large anharmonicity in the vibrational potential. (C) 2014 Elsevier B.V. All rights reserved.
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