MgCl2水溶液的太赫兹和介电光谱:使用极化模型的永久偶极子和诱导偶极子的自相关和互相关贡献。

IF 2.9 2区 化学 Q3 CHEMISTRY, PHYSICAL
Himanshu Kumar Vishwakarma,  and , Amalendu Chandra*, 
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引用次数: 0

摘要

我们利用AMOEBA极化力场对水和离子进行了分子动力学模拟,研究了MgCl2水溶液的太赫兹(THz)和介电光谱。通过从溶液的总吸收光谱中减去纯水的贡献,我们计算了三种不同浓度MgCl2的吸收光谱差异。溶液的太赫兹差谱分为离子-离子、水-水和离子-水组分,并进一步分解为自相关和互相关。通过这些解剖,我们深入了解了离子-离子和离子-水相关性以及离子引起的水-水相关性变化所产生的光谱特征。永久和诱导偶极自相关和互相关的贡献提供了对涉及阳离子-水和阴离子-水相互作用的低频振动模式的性质的进一步见解。我们的研究结果表明,水的氢键拉伸运动受到离子的抑制,而氯离子-水的氢键拉伸运动则有额外的贡献。离子-水部分的低频模式主要由阳离子-水相互作用主导。此外,低频介电谱的结果表明,在MgCl2盐的存在下,水的集体偶极子的弛豫明显减慢,这主要是由于溶液中二价Mg2+离子产生的强局部电场。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Terahertz and Dielectric Spectroscopy of Aqueous MgCl2 Solutions: Self- and Cross-Correlation Contributions of Permanent and Induced Dipoles Using Polarizable Models

Terahertz and Dielectric Spectroscopy of Aqueous MgCl2 Solutions: Self- and Cross-Correlation Contributions of Permanent and Induced Dipoles Using Polarizable Models

We have investigated the terahertz (THz) and dielectric spectra of aqueous MgCl2 solutions through molecular dynamics simulations using the AMOEBA polarizable force field for both water and ions. We calculated the differenceabsorption spectra for three different concentrations of MgCl2 by subtracting the pure water contribution from the total absorption spectra of the solutions. The difference THz spectra of the solutions are divided into ion–ion, water–water, and ion–water components, with further resolution into self- and cross-correlations. Through these dissections, we gained insights into spectral features arising from ion–ion and ion–water correlations and also from changes in water–water correlations caused by ions. The contributions of permanent and induced dipole auto- and cross-correlations provide further insights into the nature of low-frequency vibrational modes involving cation–water and anion–water interactions. Our results reveal that the hydrogen bond stretch motion of water is suppressed by ions, whereas an additional contribution comes from the chloride ion–water hydrogen bond stretch motion. The low-frequency modes in the ion–water part are found to be mainly dominated by cation–water interactions. Furthermore, the results of the low-frequency dielectric spectra show that the relaxation of the collective dipole of water is slowed significantly in the presence of MgCl2 salts, primarily due to the strong local electric fields produced by the divalent Mg2+ ions in the solutions.

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来源期刊
CiteScore
5.80
自引率
9.10%
发文量
965
审稿时长
1.6 months
期刊介绍: An essential criterion for acceptance of research articles in the journal is that they provide new physical insight. Please refer to the New Physical Insights virtual issue on what constitutes new physical insight. Manuscripts that are essentially reporting data or applications of data are, in general, not suitable for publication in JPC B.
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