Communication: Tolman length and rigidity constants of water and their role in nucleation

Wilhelmsen, Øivind; Bedeaux, Dick; Reguera, David

doi:10.1063/1.4919689

Cited by 50 publications

(29 citation statements)

References 41 publications

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“…There, δ T was computed from the tensile force of a water cylinder spanning across the simulation box with periodic boundary conditions. This value also agrees well with recent experimental [56] and theoretical [25,[57][58][59] studies. A negative Tolman length favors water cavities over droplets, tends to flatten the droplet, and thus yields a negative contribution to τ app in Eq.…”

Section: B Decomposition Of the Apparent Line Tensionsupporting

confidence: 92%

Generalized line tension of water nanodroplets

et al. 2018

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We compare all-atom simulations of nanoscale water droplets of spherical and cylindrical morphologies on flat surfaces with tunable polarities. We find that for both morphologies, the contact angle depends, albeit differently, on the droplet size, which can be well described by the modified Young equation with an apparent line tension as a fitting parameter. In order to quantify the origin of the apparent line tension, we invoke a continuum-level description of the droplets for both morphologies. This enables us to decompose the apparent line tension into individual components that stem from a contact-angle dependent line tension and the Tolman correction to the surface tension.

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Section: B Decomposition Of the Apparent Line Tensionsupporting

confidence: 92%

Generalized line tension of water nanodroplets

et al. 2018

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“…Equation 23shows that the direction of µ 2 is not fully determined by the path P, but in general also depends on the choice of dividing surface. Regarding the density profile, a curvature expansion of the identity ρ(z + (R)) = ρ(z) yields that ρ 0 (z) = ρ 0 (z + 0 ), (27)…”

Section: Role Of the Dividing Surfacementioning

confidence: 99%

“…A major reason for the interest in the curvature dependence of surface tension is that it has a significant impact on the nucleation rates predicted by Classical Nucleation Theory since it affects the work of formation for a critical cluster. 13,[19][20][21][22][23][24][25][26] For pure water droplets nucleating in supersaturated vapor, incorporating the curvature dependence of the surface tension improves the agreement between the theory and the experimental results; 27,28 the hope is that this also holds true for other substances and even for mixtures. Other applications of the Helfrich expansion include elastic properties of biological membranes, 15,29 highly curved films, 16 and wetting at the nanoscale.…”

Section: Introductionmentioning

confidence: 99%

Tolman lengths and rigidity constants of multicomponent fluids: Fundamental theory and numerical examples

Aasen

Blokhuis

Wilhelmsen

2018

The Journal of Chemical Physics

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The curvature dependence of the surface tension can be described by the Tolman length (first-order correction) and the rigidity constants (second-order corrections) through the Helfrich expansion. We present and explain the general theory for this dependence for multicomponent fluids and calculate the Tolman length and rigidity constants for a hexane-heptane mixture by use of square gradient theory. We show that the Tolman length of multicomponent fluids is independent of the choice of dividing surface and present simple formulae that capture the change in the rigidity constants for different choices of dividing surface. For multicomponent fluids, the Tolman length, the rigidity constants, and the accuracy of the Helfrich expansion depend on the choice of path in composition and pressure space along which droplets and bubbles are considered. For the hexane-heptane mixture, we find that the most accurate choice of path is the direction of constant liquid-phase composition. For this path, the Tolman length and rigidity constants are nearly linear in the mole fraction of the liquid phase, and the Helfrich expansion represents the surface tension of hexane-heptane droplets and bubbles within 0.1% down to radii of 3 nm. The presented framework is applicable to a wide range of fluid mixtures and can be used to accurately represent the surface tension of nanoscopic bubbles and droplets.

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“…There have been a number of other studies which calculated the Tolman length for water experimentally and theoretically. [21][22][23] Using MD simulations, this value is also calculated for different common water models. 24,25 These studies give the Tolman length in the order of 0.5 Å.…”

Section: Introductionmentioning

confidence: 99%

Wetting at the nanoscale: A molecular dynamics study

Khalkhali

Kazemi

Zhang

et al. 2017

The Journal of Chemical Physics

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A novel method to calculate the solid-liquid contact angle is introduced in this study. Using the 3D configuration of a liquid droplet on a solid surface, this method calculates the contact angle along the contact line and provides an angular distribution. Although this method uses the 3D configuration of liquid droplets, it does not require the calculation of the 3D density profile to identify the boundaries of the droplet. This decreases the computational cost of the contact angle calculation greatly. Moreover, no presumption about the shape of the liquid droplet is needed when using the method introduced in this study. Using this method, the relationship between the size and the contact angle of water nano-droplets on a graphite substrate was studied. It is shown that the contact angle generally decreases by increasing the size of the nano-droplet. The microscopic contact angle of 83.0° was obtained for water on graphite which is in a good agreement with previous experimental and numerical studies. Neglecting other nanoscale effects which may influence the contact angle, the line tension of SPC/E (extended simple point charge model) water was calculated to be 3.6×10 N, which is also in good agreement with the previously calculated values.

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Communication: Tolman length and rigidity constants of water and their role in nucleation

Cited by 50 publications

References 41 publications

Generalized line tension of water nanodroplets

Generalized line tension of water nanodroplets

Tolman lengths and rigidity constants of multicomponent fluids: Fundamental theory and numerical examples

Wetting at the nanoscale: A molecular dynamics study

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