Specific line shape of the lowest frequency Raman scattering modes of triethylene glycol.

Abstract

For both dielectric spectroscopy and light scattering spectra, the relaxation modes in the microwave region have been characterized by the Debye relaxation model, which is determined by the peak frequency, or by an empirically extended model (e.g., Cole-Davidson and Kohlrausch-Williams-Watts), which has the appropriate line shape. For light scattering from glass-forming liquids, the general line shape is a broader high frequency side in comparison with Debye relaxation. However, for triethylene glycol (TEG) in liquid form at room temperature, the lowest frequency Raman scattering (LFR) mode shows a peak at about 3.0GHz, which is narrower than that expected for the Debye relaxation. With increasing temperature, this peak exhibits a significant blueshift and begins to resemble the Debye relaxation shape, indicating that the LFR mode of TEG is also a relaxation mode. The narrowing of the LFR mode of TEG is suggested to be caused from the increased non-whiteness of the fluctuation correlations due to increased hydrogen bonding. This is a consequence of breaking the Debye relaxation model's approximation of the overdamping and narrowing limits in the GHz region, which was found in this study by analyzing the relaxation modes of Raman scattering using the multiple random telegraph model for evaluating thermal bath correlation. The analysis results show that the LFR relaxation times of TEG and the main dielectric relaxation overlap only by 333K. However, the second LFR mode and β-relaxation at higher frequencies coincide over a wide temperature range, suggesting that they are corresponding modes.