Surface free energy of a hard-sphere fluid at curved walls: Deviations from morphometric thermodynamics

Davidchack, Ruslan L.; Laird, Brian B.

doi:10.1063/1.5053929

Cited by 8 publications

(11 citation statements)

References 29 publications

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“…In this paper we report the results for µ ex (σ, η) which clearly show deviation from the expression (10), as well as from the general cubic polynomial dependence (2) tested by Heyes and Santos. 2 To achieve this, we have combined the results from Ref.…”

Section: Please Cite This Article Asmentioning

confidence: 64%

“…In this Section we analyse the deviation of the excess chemical potential obtained in molecular simulations from the reference expression (10), where p(η) is given by ( 12) and γ 0 (η) obtained from the precise Gibbs-Cahn measurements presented in Ref. 16.…”

Section: Analysis Of Resultsmentioning

confidence: 99%

“…Figure 5 shows the deviation of the above expression from the simulation data. The above expression is used in the reference expression (10) to which we compare the excess chemical potential simulation results presented in this work.…”

Section: Analysis Of Resultsmentioning

confidence: 99%

“…In a recent paper 10 we have presented high-precision measurements of the HS fluid surface free energy of the HS fluid at cylindrical and spherical walls of different diameters. The purpose of this work was to test the limits of applicability of the MT assumptions.…”

Section: Please Cite This Article As Doi:101063/50100073mentioning

confidence: 99%

“…. We present the differences for four different empirical expressions: a) BCSK, given by (2) with the coefficients from ( 3) and (4); b) reference expression (10); c) reference expression with the large-σ correction (17), where a 0 (η) and b 1 (η) are given by (19); d) reference expression with both large-σ and small-σ corrections (18), where the coefficients in the small-σ correction are given by (26).…”

Section: Please Cite This Article Asmentioning

confidence: 99%

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Chemical potential and surface free energy of a hard spherical particle in hard-sphere fluid over the full range of particle diameters

Davidchack

Laird

2022

The Journal of Chemical Physics

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The excess chemical potential $\mu^\mathrm{ex}(\sigma,\eta)$ of a test hard spherical particle of diameter $\sigma$ in a fluid of hard spheres of diameter $\sigma_0$ and packing fraction $\eta$ can be computed with high precision using Widom's particle insertion method [J.~Chem.~Phys.~{\bf 39}, 2808 (1963)] for $\sigma$ between 0 and just larger than 1 and/or small $\eta$. Heyes and Santos [J.~Chem.~Phys.~{\bf 145}, 214504 (2016)] showed analytically that the only polynomial representation of $\mu^\mathrm{ex}$ consistent with the limits of $\sigma$ at zero and infinity has a cubic form. On the other hand, through the solvation free energy relationship between $\mu^\mathrm{ex}$ and the surface free energy $\gamma$ of hard-sphere fluid at a hard spherical wall, we can obtain precise measurements of $\mu^\mathrm{ex}$ for large $\sigma$, extending up to infinity (flat wall) [J.~Chem. Phys.~{\bf 149}, 174706 (2018)]. Within this approach, the cubic polynomial representation is consistent with the assumptions of Morphometric Thermodynamics. In this work, we present measurements of $\mu^\mathrm{ex}$ that combine the two methods to obtain high-precision results for the full range of $\sigma$ values from zero to infinity, which show statistically significant deviations from the cubic polynomial form. We propose an empirical functional form for $\mu^\mathrm{ex}$ dependence on $\sigma$ and $\eta$ which better fits the measurement data while remaining consistent with the analytical limiting behaviour at zero and infinite $\sigma$.

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confidence: 64%

Section: Analysis Of Resultsmentioning

confidence: 99%

Section: Analysis Of Resultsmentioning

confidence: 99%

Section: Please Cite This Article As Doi:101063/50100073mentioning

confidence: 99%

Section: Please Cite This Article Asmentioning

confidence: 99%

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Chemical potential and surface free energy of a hard spherical particle in hard-sphere fluid over the full range of particle diameters

Davidchack

Laird

2022

The Journal of Chemical Physics

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Atomistic characterization of the dispersed liquid droplet in immiscible Al–Pb alloy

Liang

et al. 2021

Journal of Materials Research and Technology

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Surface Free Energy of a Hard-Disk Fluid at Curved Hard Walls: Theory and Simulation

2020

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In this work, we examine the surface thermodynamics of a hard-disk fluid at curved hard walls using Monte Carlo (MC) simulation and a generalized scaled particle theory (gSPT). The curved walls are modeled as hard disks of varying radii, R. The surface free energy, γ, and excess surface volume, v ex, for this system are calculated as functions of both the fluid packing fraction and the wall radius. The simulation results are used to test, for this system, the assumptions of morphometric thermodynamics (MT), which predicts that both γ and v ex are linear functions of the surface curvature, 1/R, for a two-dimensional system. In addition, we compare the simulation results to the gSPT developed in this work, as well as with virial expansions derived from the known virial coefficients of the binary hard-sphere fluid. At low to intermediate packing fractions, the non-MT terms (terms of higher order than 1/R in a expansion of γ and v ex) of γ are zero within the simulation error; however, at the highest densities, deviations from MT become significant, similar to what was seen in our earlier simulation work on the three-dimensional hard-sphere/hard-wall system. In addition, the new gSPT gives improved results for both γ and v ex over standard scaled particle theory (SPT) but underestimates the deviations from MT at high density.

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Surface free energy of a hard-sphere fluid at curved walls: Deviations from morphometric thermodynamics

Cited by 8 publications

References 29 publications

Chemical potential and surface free energy of a hard spherical particle in hard-sphere fluid over the full range of particle diameters

Chemical potential and surface free energy of a hard spherical particle in hard-sphere fluid over the full range of particle diameters

Atomistic characterization of the dispersed liquid droplet in immiscible Al–Pb alloy

Surface Free Energy of a Hard-Disk Fluid at Curved Hard Walls: Theory and Simulation

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