Reversal of the Temperature Dependence of Hydrophobic Hydration in Supercooled Water

Ashbaugh, Henry S.

doi:10.1021/acs.jpclett.1c02399

Cited by 4 publications

(8 citation statements)

References 26 publications

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“…Also, in Figure 4 , we compared our results to another TIP4P/2005 MD simulations in the liquid water range for Ar. 33 In this simulational study, solutes were modeled using LJ potentials optimized to reproduce the experimentally known hydration free energy at 25° C and 1 bar. 34 We found that our predictions for the hydration free energy are very close to their results for Ar taken as an LJ particle but with a slightly different curvature, which results in some deviation for the hydration enthalpy and hydration entropy.…”

Section: Resultsmentioning

confidence: 99%

“…Also, in Figure , we compared our results to another TIP4P/2005 MD simulations in the liquid water range for Ar . In this simulational study, solutes were modeled using LJ potentials optimized to reproduce the experimentally known hydration free energy at 25° C and 1 bar .…”

Section: Resultsmentioning

confidence: 99%

“…Figure 4. Temperature dependence of thermodynamic quantities for Ar, comparing our Crustwater theory (black lines) with experiments (red triangles, with line fit) and Ashbaugh et al MD data (green squares, with line fit) 33. …”

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confidence: 99%

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Crustwater: Modeling Hydrophobic Solvation

et al. 2022

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We describe Crustwater, a statistical mechanical model of nonpolar solvation in water. It treats bulk water using the Cage Water model and introduces a crust , i.e., a solvation shell of coordinated partially structured waters. Crustwater is analytical and fast to compute. We compute here solvation vs temperature over the liquid range, and vs pressure and solute size. Its thermal predictions are as accurate as much more costly explicit models such as TIP4P/2005. This modeling gives new insights into the hydrophobic effect: (1) that oil–water insolubility in cold water is due to solute–water (SW) translational entropy and not water–water (WW) orientations, even while hot water is dominated by WW cage breaking, and (2) that a size transition at the Angstrom scale, not the nanometer scale, takes place as previously predicted.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Crustwater: Modeling Hydrophobic Solvation

et al. 2022

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“…Interestingly, eq largely relies only on water’s macroscopic equation-of-state, while the structure of water is primarily embodied within d ww (assumed here to be 2.65 Å). This diameter has been found to be effectively independent of temperature. , The integrated pair-correlation structure of water is incorporated into the theory through its compressibility as determined by Kirkwood-Buff theory, although this plays a secondary role to d ww . In previous studies, non-Gaussian fluctuations were found to become more significant as the size of the solute grows. ,, As such, IGFT is expected to become increasingly inaccurate for meso-scale and larger solute volumes.…”

Section: Theorymentioning

confidence: 99%

Gaussian and Non-Gaussian Solvent Density Fluctuations within Solute Cavities in a Water-like Solvent

Ashbaugh

2023

J. Chem. Theory Comput.

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We report a Monte Carlo simulation study of length-scale-dependent density fluctuations in cavities in the coarse-grained mW representation of water at ambient conditions. Specifically, we use a combination of test particle insertion and umbrella sampling techniques to examine the full range of water occupation states in spherical cavities up to 6.3 Å radius in water. As has previously been observed, water density fluctuations are found to be effectively Gaussian in nature for atomic-scale cavities, but as the cavities get larger, they exhibit a non-Gaussian “fat-tail” distribution for lower occupancy states. We introduce a new statistical thermodynamic approach to analyze non-Gaussian fluctuations based on the radial distribution of waters about cavities with varying numbers of waters within its boundaries. It is shown that the onset of these non-Gaussian fluctuations is a result of the formation of a bubble within the cavity as it is emptied, which is accompanied by the adsorption of waters onto its interior surface. We revisit a theoretical framework we previously introduced to describe Gaussian fluctuations within cavities to incorporate bubble formation by including surface tension contributions. This modified theory accurately describes density fluctuations within both atomic and meso-scale cavities. Moreover, the theory predicts the transition from Gaussian to non-Gaussian fluctuations at a specific cavity occupancy, in excellent agreement with simulation observations.

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“… (Left) Dimensionless isobaric solvation entropy , with k B the Boltzmann constant, as a function of temperature T at atmospheric pressure for an “argon-like” solute in TIP4P/2005 water. 4 (Right) Isobaric thermal expansivity α p of TIP4P/2005 water in the same T interval. 1 …”

Section: Water As a Solventmentioning

confidence: 99%

Water’s Unusual Thermodynamics in the Realm of Physical Chemistry

Cerdeiriña

2022

J. Phys. Chem. B

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While it is known since the early work by Edsall, Frank and Evans, Kauzmann, and others that the thermodynamics of solvation of nonpolar solutes in water is unusual and has implications for the thermodynamics of protein folding, only recently have its connections with the unusual temperature dependence of the density of solvent water been illuminated. Such density behavior is, in turn, one of the manifestations of a nonstandard thermodynamic pattern contemplating a second, liquid–liquid critical point at conditions of temperature and pressure at which water exists as a deeply supercooled liquid. Recent experimental and computational work unambiguously points toward the existence of such a critical point, thereby providing concrete answers to the questions posed by the 1976 pioneering experiments by Speedy and Angell and the associated “liquid–liquid transition hypothesis” posited in 1992 by Stanley and co-workers. Challenges of this phenomenology to the branch of Statistical Mechanics remain.

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Reversal of the Temperature Dependence of Hydrophobic Hydration in Supercooled Water

Cited by 4 publications

References 26 publications

Crustwater: Modeling Hydrophobic Solvation

Crustwater: Modeling Hydrophobic Solvation

Gaussian and Non-Gaussian Solvent Density Fluctuations within Solute Cavities in a Water-like Solvent

Water’s Unusual Thermodynamics in the Realm of Physical Chemistry

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