Geethu P M, Ranganathan Venketesh T, Satapathy Dillip K
Soft Materials Laboratory, Department of Physics, Indian Institute of Technology Madras, 600036, India.
J Phys Condens Matter. 2018 Aug 8;30(31):315103. doi: 10.1088/1361-648X/aacf2c. Epub 2018 Jun 26.
Intermolecular hydrogen bonds play a crucial role in determining the unique characteristics of liquid water. We present low-frequency (1 Hz-40 MHz) dielectric spectroscopic investigations on water in the presence and absence of added solutes at different temperatures from 10 °C to 60 °C. The intersection points of temperature dependent permittivity contours at the vicinity of isopermitive frequency (IPF) in water are recorded and its properties are presumed to be related to the extent of hydrogen bond networks in water. IPF is defined as the frequency at which the relative permittivity of water is almost independent of temperature. The set of intersection points of temperature dependent permittivity contours at the vicinity of IPF are characterized by the mean [Formula: see text] and root-mean-square deviation/standard deviation [Formula: see text] associated with IPF. The tunability of M by the addition of NaCl and MgCl salt emphasizes the strong correlation between the concentration of ions in water and the M . The [Formula: see text] is surmised to be related to the orientational correlations of water dipoles as well as to the intermolecular hydrogen bond networks in water. Further, alterations in [Formula: see text] is observed with the addition of kosmotropic and chaotropic solutes into water and are thought to arise due to the restructuring of hydrogen bond networks in water in presence of added solutes. Notably, the solute induced reconfiguration of hydrogen bond networks in water or often-discussed structure making/breaking effects of the added solutes in water can be inferred, albeit qualitatively, by examining the M and [Formula: see text]. Further, the Gaussian deconvoluted OH-stretching modes present in the Raman spectra of water and aqueous solutions of IPA and DMF strongly endorses the structural rearrangements occurring in water in presence of kosmotropes and chaotropes and are in line with the results derived from the root-mean-square deviation in IPF.
分子间氢键在决定液态水的独特性质方面起着至关重要的作用。我们展示了在10℃至60℃的不同温度下,在有无添加溶质的情况下对水进行的低频(1Hz - 40MHz)介电谱研究。记录了水在等电容率频率(IPF)附近与温度相关的电容率等值线的交点,并推测其性质与水中氢键网络的程度有关。IPF定义为水的相对电容率几乎与温度无关时的频率。在IPF附近与温度相关的电容率等值线的交点集由与IPF相关的均值[公式:见文本]和均方根偏差/标准差[公式:见文本]来表征。通过添加NaCl和MgCl盐对M的可调性强调了水中离子浓度与M之间的强相关性。推测[公式:见文本]与水偶极子的取向相关性以及水中的分子间氢键网络有关。此外,向水中添加促溶剂和离液剂溶质时观察到[公式:见文本]的变化,并且认为这是由于添加溶质时水中氢键网络的重构所致。值得注意的是,通过检查M和[公式:见文本],尽管是定性地,但可以推断出溶质诱导的水中氢键网络的重新配置或通常讨论的添加溶质在水中的结构形成/破坏效应。此外,水、IPA和DMF水溶液的拉曼光谱中存在的高斯去卷积OH伸缩模式有力地支持了在存在促溶剂和离液剂时水中发生的结构重排,并且与从IPF中的均方根偏差得出的结果一致。