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块状水的玻璃化转变和弛豫行为及其与受限水的可能关系。

The glass transition and relaxation behavior of bulk water and a possible relation to confined water.

机构信息

Department of Applied Physics, Chalmers University of Technology, SE-412 96 Göteborg, Sweden.

出版信息

J Chem Phys. 2010 Jan 7;132(1):014508. doi: 10.1063/1.3285286.

Abstract

Due to the widespread importance of water and the difficulty to study it in the so-called no man's land between 150 and 235 K, deeply supercooled bulk water is currently heavily debated. It speculates about its properties from extrapolations of experimental data on bulk water above 235 K and below 150 K, computer simulations, and experiments on confined water for which the finite size effects may prevent crystallization in the no man's land. However, it is far from obvious how experimental data on bulk water should be extrapolated to the temperature range of the no man's land or how relevant results from computer simulations and studies of confined water are for bulk water. In this paper the structural and dynamical properties of supercooled bulk water are tried to be understood from experimental results on confined water and comparisons with bulk water. We propose that a similar crossover from a high temperature alpha-relaxation to a low temperature beta-relaxation occurs also for bulk water but at a higher temperature than for confined water due to the larger average number of hydrogen bonds between the water molecules in bulk water. In the case of bulk water the crossover is expected to occur around the critical temperature T(s) approximately 228 K when the buildup of an icelike tetrahedral network structure is completed. The proposed interpretation is the simplest one that is able to explain many of the peculiar properties of supercooled water.

摘要

由于水的广泛重要性以及在 150 到 235 K 之间所谓的无人区中研究它的困难,深度过冷的大块水目前受到了广泛的争论。它从高于 235 K 和低于 150 K 的大块水的实验数据、计算机模拟以及受限水的实验推断其性质,在受限水中,有限的尺寸效应可能会阻止在无人区中结晶。然而,将大块水的实验数据外推到无人区的温度范围以及将计算机模拟和受限水研究的相关结果应用于大块水的方法远非显而易见。在本文中,试图从受限水的实验结果以及与大块水的比较中理解过冷大块水的结构和动力学性质。我们提出,对于大块水也会发生从高温α弛豫到低温β弛豫的类似交叉,但由于大块水中水分子之间氢键的平均数量较大,交叉发生的温度高于受限水。在大块水的情况下,当完成冰状四面体网络结构的构建时,预计交叉会发生在大约 228 K 的临界温度 T(s)左右。所提出的解释是最简单的解释,能够解释许多过冷水的特殊性质。

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