Reorientational Relaxation of Small Solutes in Viscoelastic Liquids

Yamaguchi, Tsuyoshi; Abe, Yusuke; Nishiyama, Katsura

doi:10.1021/acs.jpcb.6b00365

Cited by 4 publications

(7 citation statements)

References 38 publications

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“…A classical, and rather simple, model is the small‐step rotational diffusion model based on the Debye diffusion picture, in which the reorientation proceeds through a sequence of very small jumps. It was later on demonstrated that this picture is more applicable to the motion of macromolecules, but not that much to the water molecules (Bagchi, ; Banerjee & Bagchi, ; Laage, ; Laage & Hynes, ; Yamaguchi, Abe, & Nishiyama, ; Zasetsky, Petelina, Lyashchenko, & Lileev, ; Q. Zhang, Chen, et al, ; Q. Zhang, Wu, et al, ). A second picture is the so‐called “flickering cluster” mechanism (Eisenberg & Kauzmann, ), which assumes the formation of hydrogen bonds in water to be cooperative.…”

Section: Studying Water Reorientation Dynamics Based On the Theoretical Modelingmentioning

confidence: 99%

Ion effect on the dynamics of water hydrogen bonding network: A theoretical and computational spectroscopy point of view

Zhang

et al. 2018

WIREs Comput Mol Sci

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Understanding the elementary hydration dynamics of the ions and their couplings with the aqueous environments is important for researches in fields including energy, molecular biology, biomedical sciences, and chemical reactions. The concept of hydration shell is ubiquitously used to rationalize the differences of water behavior near the ions with respect to those in the bulk water. One intriguing issue, however, is to decide the spatial range of these hydration shells. Different experimental spectroscopic techniques such as the femtosecond infrared at high frequency and optical Kerr effect, dielectric relaxation, as well as terahertz measurements at low frequency often give controversial indications on this matter. As the optical transition observables provided by the spectroscopic measurements only indirectly reflect the realspace structure and dynamics information, the theoretical modeling of these signals is often desired in order to reveal the underlying physics in each of these measurements, and to understand the aforementioned apparent controversy. In this review, we outline recent progresses in the theoretical modeling of water dynamics around the ions and ionic moieties and the related vibrational spectroscopy, especially on the femtosecond infrared related single molecular water reorientation and the lowfrequency vibrational spectra related collective water dynamics. This article is categorized under: Theoretical and Physical Chemistry > Spectroscopy Theoretical and Physical Chemistry > Statistical Mechanics K E Y W O R D S hydrogen bond relaxation, ion effect, ionic solution, jump reorientation, molecular dynamic simulation, nonlinear spectroscopy

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Section: Studying Water Reorientation Dynamics Based On the Theoretical Modelingmentioning

confidence: 99%

Ion effect on the dynamics of water hydrogen bonding network: A theoretical and computational spectroscopy point of view

Zhang

et al. 2018

WIREs Comput Mol Sci

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“…The Journal of Physical Chemistry B pubs.acs.org/JPCB Article reported in a wide range of alkane solvents, 128−130 as well as rotation times in a few normal alcohols 42,99 and alkanes 42,99 reveal benzene motions that are up to 2-fold faster than predicted by the above correlations. Departures of this magnitude are not surprising and may be attributed to variations in a number of molecular features of the solvent such as size, 50,96,97 free volume, 98 and solute−solvent attractions.…”

Section: Discussionmentioning

confidence: 79%

“…Comparable decreases in τ B are also observed in the series of normal alcohols methanol to 1dodecanol, but not in bulk water or in ethylene glycol. Collectively, these observations suggest that solvent characteristics other than viscosity, for example, the solvent size, 50,96,97 free volume, 98 or viscoelasticity 99 are important in determining the friction on benzene. However, the similar values of τ B in isoviscous alkanes and normal alcohols, as well as the comparable values of both D B and τ B in aprotic solvents of similar viscosity but widely differing polarities (Table 1), suggest that electrostatic interactions with solvent contribute little to the friction on benzene motions.…”

Section: Diffusion Coefficients and Rotational Correlation Timesmentioning

confidence: 97%

Do Electrostatics Control the Diffusive Dynamics of Solitary Water? NMR and MD Studies of Water Translation and Rotation in Dipolar and Ionic Solvents

Mukherjee,

Palchowdhury,

Maroncelli

2024

J. Phys. Chem. B

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NMR-based measurements of the diffusion coefficients and rotation times of solitary water and benzene at 300 K are reported in a diverse collection of 13 conventional organic solvents and 10 imidazolium ionic liquids. Proton chemical shifts of water are found to be correlated to water OH-stretching frequencies, confirming the importance of electrostatic interactions in these shifts. However, the influence of magnetic interactions in aromatic solvents renders chemical shifts a less reliable indicator of electrostatics. Diffusion coefficients (D B ) and rotational correlation times (τ B ) of benzene in the solvents examined are accurately described as functions of viscosity (η) by D B ∝ η −0.81 and τ B ∝ η 0.64 . Literature values of D B and τ B in alkane and normal alcohols, which were not included among the solvents studied here, are systematically faster than predicted by these correlations, indicating that factors beyond solvent viscosity play a role in determining the friction on benzene. In contrast to benzene, water diffusion and rotation are poorly described in terms of viscosity alone, even in the dipolar and ionic solvents measured here. The present data and the substantial literature data already available on dilute water diffusion show a systematic dependence of D W on solvent polarity among isoviscous solvents. The aspect of solvent polarity most relevant to water dynamics is the ability of a solvent to accept hydrogen bonds from water, as conveniently quantified by the frequency of water's OH stretching band, Δν OH . The friction on translation, ζ tr = k B T/D W , and rotation, ζ rot = k B Tτ W , are both well correlated by functions of the form ζ(η, Δν OH ) = a 1 η a 2 exp (a 3 Δν OH ), where the a i are adjustable parameters. Molecular dynamics simulations reveal a strong coupling between electrostatic and nonelectrostatic water-solvent interactions, which makes it impossible to dissect the friction on water into additive dielectric and hydrodynamic components. Simulations also provide a tentative explanation for the unusual form of the correlating function ζ(η, Δν OH ), at least in the case of ζ rot .

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“…Here, it is noteworthy that the high-frequency extension of the QCM-D measurement achieved in this work enables the observation of the viscoelastic relaxation of ethylene glycol-no relaxation was found in the frequency range of our conventional QCM-D measurement up to 200 MHz. 3) The results of two room-temperature ionic liquids [emim] [TFSA] and [omim][TFSA] are plotted in Fig. 7.…”

Section: Viscoelastic Relaxation Of Viscous Liquidsmentioning

confidence: 99%

“…Therefore, the measurement of the frequency-dependent complex shear viscosity gives information on the time scale of microscopic dynamics, which might also be related to the dynamic solvent effects on fast molecular motion and chemical reaction. 3,4) Measurement below the kHz frequency regime is possible with commercially available mechanical rheometers, and it is routinely applied to soft materials such as polymer systems, surfactant solutions, and colloidal dispersions. However, the frequency range of mechanical rheometers is limited up to the kHz regime, and the rheometers cannot measure viscoelastic relaxation of low molecular weight liquids far from the glass transition.…”

Section: Introductionmentioning

confidence: 99%

Measurement of complex shear viscosity up to 3 GHz using an electrodeless AT-cut quartz transducer

Yamaguchi¹,

Matsuoka²

2022

Jpn. J. Appl. Phys.

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An experimental method is proposed to determine the frequency-dependent complex shear viscosity of liquids based on the quartz crystal microbalance with dissipation method. An AT-cut quartz transducer without metal electrodes is immersed in a sample liquid and the transducer is electrically coupled to the circuit through the dielectric response of the sample itself. After correcting for the apparent change in the resonance properties due to the dielectric coupling of the sample, our method is able to determine the viscosity of liquids of high polarity and low viscosity at frequencies as high as 3 GHz. The method was then applied to ethylene glycol and the viscoelastic relaxation in the GHz regime was observed. Furthermore, it was also applied to room-temperature ionic liquids to show that the dielectric correction of the resonance properties is valid for conductive liquids.

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Reorientational Relaxation of Small Solutes in Viscoelastic Liquids

Cited by 4 publications

References 38 publications

Ion effect on the dynamics of water hydrogen bonding network: A theoretical and computational spectroscopy point of view

Ion effect on the dynamics of water hydrogen bonding network: A theoretical and computational spectroscopy point of view

Do Electrostatics Control the Diffusive Dynamics of Solitary Water? NMR and MD Studies of Water Translation and Rotation in Dipolar and Ionic Solvents

Measurement of complex shear viscosity up to 3 GHz using an electrodeless AT-cut quartz transducer

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