Kim Chae Un, Tate Mark W, Gruner Sol M
Cornell High Energy Synchrotron Source (CHESS) and Macromolecular Diffraction Facility at CHESS (MacCHESS), Cornell University, Ithaca, NY 14853; Department of Physics, Ulsan National Institute of Science and Technology, Ulsan 689-798, Republic of Korea;
Laboratory of Atomic and Solid State Physics, Cornell University, Ithaca, NY 14853;
Proc Natl Acad Sci U S A. 2015 Sep 22;112(38):11765-70. doi: 10.1073/pnas.1510256112. Epub 2015 Sep 8.
Observation of theorized glass-to-liquid transitions between low-density amorphous (LDA) and high-density amorphous (HDA) water states had been stymied by rapid crystallization below the homogeneous water nucleation temperature (∼235 K at 0.1 MPa). We report optical and X-ray observations suggestive of glass-to-liquid transitions in these states. Crack healing, indicative of liquid, occurs when LDA ice transforms to cubic ice at 160 K, and when HDA ice transforms to the LDA state at temperatures as low as 120 K. X-ray diffraction study of the HDA to LDA transition clearly shows the characteristics of a first-order transition. Study of the glass-to-liquid transitions in nanoconfined aqueous solutions shows them to be independent of the solute concentrations, suggesting that they represent an intrinsic property of water. These findings support theories that LDA and HDA ice are thermodynamically distinct and that they are continuously connected to two different liquid states of water.
在低于均匀水成核温度(0.1MPa下约235K)时,快速结晶阻碍了对低密度非晶态(LDA)和高密度非晶态(HDA)水状态之间理论上的玻璃态到液态转变的观察。我们报告了表明这些状态下玻璃态到液态转变的光学和X射线观察结果。当LDA冰在160K转变为立方冰时,以及当HDA冰在低至120K的温度下转变为LDA状态时,会出现表明液态的裂纹愈合现象。对HDA到LDA转变的X射线衍射研究清楚地显示了一级转变的特征。对纳米受限水溶液中玻璃态到液态转变的研究表明,它们与溶质浓度无关,这表明它们代表了水的一种固有特性。这些发现支持了以下理论:LDA和HDA冰在热力学上是不同的,并且它们与水的两种不同液态连续相连。