Department of Chemical Engineering and Biotechnology, University of Cambridge, New Museums Site, Pembroke Street, Cambridge, CB2 3RA, UK.
Phys Chem Chem Phys. 2013 Jul 28;15(28):11931-42. doi: 10.1039/c3cp51936h. Epub 2013 Jun 14.
The absorption spectra of D-sorbitol and a range of its concentrated aqueous solutions were studied by terahertz spectroscopy over the temperature interval of 80 K < T < 310 K. It is shown that the slow-down of molecules at around the glass transition temperature, Tg, dramatically influences the thermal dependence of the absorption at terahertz frequencies. Furthermore, two different absorption regimes are revealed below Tg: at temperatures well below Tg, the absorption resembles the coupling of terahertz radiation to the vibrational density of states (VDOS); above these temperatures, between 160 K and Tg, in the sample of pure sorbitol and the sample of a solution of 70 wt% sorbitol in water, another type of absorption is observed at terahertz frequencies. Several possibilities of the physical origin of this absorption are discussed and based on the experimental data this process is tentatively assigned to the Johari-Goldstein β-relaxation processes shifting to lower frequencies at temperatures below Tg leaving behind a spectrum largely dominated by losses into the VDOS.
研究了 D-山梨醇及其一系列浓水溶液在 80 K < T < 310 K 温度范围内的太赫兹光谱吸收谱。结果表明,分子在玻璃化转变温度 Tg 附近的减速对太赫兹频率处吸收的热依赖性有显著影响。此外,在 Tg 以下揭示了两种不同的吸收模式:在远低于 Tg 的温度下,吸收类似于太赫兹辐射与振动态密度(VDOS)的耦合;在这些温度以上,在纯山梨醇样品和 70wt%山梨醇水溶液的样品中,在 160 K 到 Tg 之间的温度范围内,在太赫兹频率处观察到另一种类型的吸收。讨论了这种吸收的几种可能的物理起源,并基于实验数据,将该过程暂时归因于 Johari-Goldstein β弛豫过程向低于 Tg 的温度转移,从而在 VDOS 主导的光谱中留下大量损耗。