论文标题

液态水的NIR光谱的温度依赖性分析证实存在两个阶段,其中之一是连贯的状态

Temperature Dependence Analysis of the NIR Spectra of Liquid Water confirms the existence of two phases, one of which is in a coherent state

论文作者

Renati, Paolo, Kovacs, Zoltan, De Ninno, Antonella, Tsenkova, Roumiana

论文摘要

液态水的IR和NIR光谱中的同性(相等吸收)点是一个众所周知的特征,它们见证了探测系统中两个振荡器的存在。尽管这是一个众所周知的实验事实,但在主流分子动力学方法中,提出的理论解释无法阐明这是为什么这种切断频率确实存在的物理原因。我们研究了纯Milli-Q水,以增加Vis-NIR范围(400-2500 nm)的温度。我们特别注意了观察到同级点的oh-bond伸展模式的第一个泛质区域(1300-1600 nm)。第二个衍生化分析清楚地显示了两种模式,可以将它们分配给参与不同氢键构型的水分子,这些氢键相对丰度受温度控制。我们还观察到,这些模式的比率与霍夫的行为相比,支持其能量差(能隙)在温度下是独立的。此外,对数库的图显示了种群比率相对于扰动(温度)的规模不变性,这证实了液体中远距离的动力学的存在。我们表明,可以将从实验数据估计的能量和熵之间的两个阶段差异与量子电动动力学(QED)的预测进行比较。

Isosbestic (equal absorption) points in the IR and NIR spectra of liquid water are a well known feature and they witness the existence of two populations of oscillators in the probed system. Despite it is a well known experimental fact, in the mainstream molecular dynamics approach the proposed theoretical explanations for it are not able to elucidate which is the physical reason why such a cut off frequency (at the isosbestic point) does exist. We investigate pure Milli-Q water on increasing the temperature in the vis-NIR range (400-2500 nm). We specifically payed attention to the first overtone region (1300-1600 nm) of the OH-bond stretching-mode where an isosbestic point has been observed. A second derivative analysis clearly shows two modes, which can be assigned to water molecules involved in different hydrogen bonding configurations whose relative abundance is controlled by the temperature. We have also observed that the ratio of these modes follows a van't Hoff behavior supporting that their energy difference (energy gap) is independent on the temperature. Furthermore, a log-log plot shows a scale invariance of the population ratio with respect to the perturbation (temperature), confirming the existence of a long range correlated dynamics in the liquid. We show that the two phases differences between energy and entropy estimated from the experimental data can be compared with the predictions of Quantum Electro Dynamics (QED) showing a remarkable agreement.

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