Non-monotonic composition dependence of the breakdown of Stokes–Einstein relation for water in aqueous solutions of ethanol and 1-propanol: explanation using translational jump-diffusion approach

Dueby, Shivam; Dubey, Vikas; Indra, Sandipa; Daschakraborty, Snehasis

doi:10.1039/d2cp02664c

Cited by 13 publications

(34 citation statements)

References 152 publications

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“…To see that, we calculate the H-bond dynamics. We use the following equation to compute the intermittent H-bond correlation functions C HB ( t ). ,,− C HB ( t ) = ⟨ h false( 0 false) h false( t false) ⟩ / ⟨ h ⟩ …”

Section: Resultsmentioning

confidence: 99%

“…The decays of C HB ( t ) are shown in Figure S6 for all the systems at different temperatures. The function C HB ( t ) is fit with a tri-exponential function. , C HB ( t ) = a 1 exp ( − t / τ 1 ) + a 2 0.25em exp ( − t / τ 2 ) + a 3 0.25em exp ( − t / τ 3 ) ; a 1 + a 2 + a 3 = 1 …”

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

“…It was observed earlier that residual diffusion is coupled to the viscosity of the medium fairly strongly irrespective of temperature and pressure variation or presence of other solvents (alcohol), etc. 41 Now we turn our focus to the CSE relation proposed for evaluating the viscosity of confined liquid. Simonnin et al 53 proposed an analytical equation for the lateral diffusion coefficient D ∥ as a function of liquid height d and lateral size of the box L assuming a no-slip boundary condition on the walls.…”

Section: Resmentioning

confidence: 99%

“…However, this is not always true. Some of the circumstances when the SE relation is not completely obeyed include water in confinement, , water in a supercooled state, ,,− water under high pressure, and the presence of another solvent. − Therefore, some modification(s) of the existing CSE approach are necessary for a more robust estimation of viscosity of water in different scenarios.…”

Section: Introductionmentioning

confidence: 99%

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What Is the Viscosity of Liquid Water Confined in a Hydrophobic Nanotube? Estimation Using a Novel Approach

Khan

Daschakraborty

2023

J. Phys. Chem. C

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Computation of the shear viscosity (η) of liquid water under nanoconfinement is a daunting task, albeit crucial in different areas related to nanofluidics. The viscosity of bulk water is computed using the Green–Kubo formula or Stokes–Einstein (SE) relation. However, these relations are less useful in the case of water confined in a cylindrical nanotube since the stress tensors are asymmetric and the SE relation breaks down. Using a novel method, based on the translational Jump-corrected Confined Stokes–Einstein (JCSE) relation that takes into account the breakdown of the SE relation, we compute the viscosity of water inside some hydrophobic carbon nanotubes (CNTs) in a wide range of temperatures including the supercooled regime. The viscosity of water in narrow CNT(10,10) is seen to be surprisingly higher compared to bulk water at the same thermodynamic condition. This contradicts the usual notion and the past theoretical observations suggesting significantly low viscosity of water inside hydrophobic CNTs.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Resmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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What Is the Viscosity of Liquid Water Confined in a Hydrophobic Nanotube? Estimation Using a Novel Approach

Khan

Daschakraborty

2023

J. Phys. Chem. C

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Thermodynamic response functions and Stokes-Einstein breakdown in superheated water under gigapascal pressure

et al. 2023

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Liquid water is the most intriguing liquid in nature, both because of its importance to every known form of life, and its numerous anomalous properties, largely magni ed under supercooled conditions. Among the anomalous properties of water is the seeming divergence of the thermodynamic response functions and dynamic properties below the homogenous nucleation temperature (~232 K). Furthermore, water exhibits an increasingly decoupling of the viscosity and diffusion, upon cooling, resulting in the breakdown of the Stokes-Einstein relationship (SER). At high temperatures and pressures, however, water behaves more like a "simple" liquid. Nonetheless, experiments at 400 K and GPa pressures (Bove et al. (2011) Phys. Rev. Lett., 111:185901) showed that although the diffusion decreases monotonically with the pressure, opposite to pressurized supercooled water, a decoupling of the viscosity and diffusion, larger than that found in supercooled water at normal pressure, is observed. Here, we studied the thermodynamic response functions and breakdown of the SER along the 400 K isotherm up to 3 GPa, through molecular dynamics. Seven water models were investigated. A monotonic increase of the density (~50 %) and decrease of the isothermal compressibility (~90 %) and thermal expansion (~65 %) is found. Our results also show that compressed hot water has various resemblances to cool water at normal pressure, with pressure inducing the formation of a new second coordination sphere and a monotonic decrease of the diffusion and viscosity coe cients. Whereas all water models provide a good account of the viscosity, the magnitude of the violation of the SER at high pressures (> ~1 GPa) is signi cantly smaller than that found through experiments. Thus, violation of the SER in simulations is comparable to that observed for liquid supercooled water, indicating possible limitations of the water models to account for the local structure and self-diffusion of superheated water above ~1 GPa.

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Size dependence of solute’s translational jump-diffusion in solvent: Relationship between trapping and jump-diffusion

Dueby

Daschakraborty

2022

Chemical Physics Letters

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Non-monotonic composition dependence of the breakdown of Stokes–Einstein relation for water in aqueous solutions of ethanol and 1-propanol: explanation using translational jump-diffusion approach

Abstract: A series of experimental and simulation studies examined the validity of the Stokes-Einstein relationship (SER) of water in binary water/alcohol mixtures of different mixture compositions. These studies revealed a strong...

Cited by 13 publications

References 152 publications

What Is the Viscosity of Liquid Water Confined in a Hydrophobic Nanotube? Estimation Using a Novel Approach

What Is the Viscosity of Liquid Water Confined in a Hydrophobic Nanotube? Estimation Using a Novel Approach

Thermodynamic response functions and Stokes-Einstein breakdown in superheated water under gigapascal pressure

Size dependence of solute’s translational jump-diffusion in solvent: Relationship between trapping and jump-diffusion

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