Department of Bioengineering, University of California, Berkeley, CA 94720, USA.
Proc Natl Acad Sci U S A. 2010 Aug 10;107(32):14003-7. doi: 10.1073/pnas.1006599107. Epub 2010 Jul 20.
Structural polyamorphism has been promoted as a means for understanding the anomalous thermodynamics and dynamics of water in the experimentally inaccessible supercooled region. In the metastable liquid region, theory has hypothesized the existence of a liquid-liquid critical point from which a dividing line separates two water species of high and low density. A recent small-angle X-ray scattering study has claimed that the two structural species postulated in the supercooled state are seen to exist in bulk water at ambient conditions. We analyze new small-angle X-ray scattering data on ambient liquid water taken at third generation synchrotron sources, and large 32,000 water molecule simulations using the TIP4P-Ew model of water, to show that the small-angle region measures standard number density fluctuations consistent with water's isothermal compressibility temperature trends. Our study shows that there is no support or need for heterogeneities in water structure at room temperature to explain the small-angle scattering data, as it is consistent with a unimodal density of the tetrahedral liquid at ambient conditions.
结构多态性被认为是理解实验上无法获得的过冷水区中水的异常热力学和动力学的一种手段。在亚稳液相区,理论假设存在一个液相-液相临界点,从该点分出一条分界线,将高密度和低密度两种水物种分开。最近的一项小角 X 射线散射研究声称,在过冷状态下假设的两种结构物种在环境条件下的体相水中存在。我们分析了在第三代同步加速器源上获得的关于环境液态水的新小角 X 射线散射数据,以及使用 TIP4P-Ew 水模型的 32000 个水分子的大模拟,以表明小角区域测量的标准数密度波动与水的等温压缩性温度趋势一致。我们的研究表明,没有必要或需要在室温下对水结构的非均相性进行解释,以解释小角散射数据,因为它与环境条件下四面体形液体的单峰密度一致。