Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6473, USA.
Phys Chem Chem Phys. 2013 Jul 14;15(26):10732-9. doi: 10.1039/c3cp51355f. Epub 2013 May 20.
Aqueous solutions of lithium chloride are uniquely similar to pure water in the parameters such as glass transition temperature, Tg, yet they could be supercooled without freezing down to below 200 K even in the bulk state. This provides advantageous opportunity to study low-temperature dynamics of water molecules in water-like environment in the bulk rather than nano-confined state. Using high-resolution neutron spin-echo data, we argue that the critical temperature, Tc, which is also common between lithium chloride aqueous solutions and pure water, is associated with the split of a secondary relaxation from the main structural relaxation on cooling down. Our results do not allow distinguishing between a well-defined separate secondary relaxation process and the "excess wing" scenario, in which the temperature dependence of the secondary relaxation follows the main relaxation. Importantly, however, in either of these scenarios the secondary relaxation is associated with density-density fluctuations, measurable in a neutron scattering experiment. Neutron scattering could be the only experimental technique with the capability of providing information on the spatial characteristics of the secondary relaxation through the dependence of the signal on the scattering momentum transfer. We propose a simple method for such analysis.
氯化锂的水溶液在玻璃化转变温度 Tg 等参数上与纯水非常相似,但即使在大块状态下,它们也可以过冷而不冻结到 200 K 以下。这为在类似于水的环境中而不是在纳米受限状态下研究低温下水分子的动力学提供了有利的机会。使用高分辨率的中子自旋回波数据,我们认为临界温度 Tc 也存在于氯化锂水溶液和纯水中,它与次级弛豫从主结构弛豫在冷却过程中分裂有关。我们的结果不允许区分明确的单独的次级弛豫过程和“过剩翼”情景,在这种情况下,次级弛豫的温度依赖性遵循主弛豫。然而,重要的是,无论在这两种情况中的哪一种中,次级弛豫都与密度-密度涨落有关,这在中子散射实验中是可以测量的。中子散射可能是唯一具有通过信号对散射动量转移的依赖性提供关于次级弛豫空间特征的信息的实验技术。我们提出了一种简单的分析方法。