Interfacial properties of binary mixtures of simple fluids and their relation to the phase diagram

Stephan, Simon; Hasse, Hans

doi:10.1039/d0cp01411g

Cited by 38 publications

(74 citation statements)

References 122 publications

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“…Rather, the inhomogeneous distributions are best described as regulator enrichment at the interface of the dense and bulk phases. This interfacial enrichment of the regulator (i.e., lower T c ) species was also observed in the particle systems with ε DR = 0.8 at T = 0.65 (Figure S5b, but not at T > 0.8), and has been reported in previous studies of mixtures of Lennard‐Jones particles 24,25,31,32 . (As ε DR was further decreased for the particle systems, we also observed their demixing to form distinct dense phases.)…”

Section: Resultssupporting

confidence: 87%

Macromolecular regulators have matching effects on the phase equilibrium and interfacial tension of biomolecular condensates

Mazarakos

Zhou

2021

Protein Science

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The interfacial tension of phase‐separated biomolecular condensates affects their fusion and multiphase organization, and yet how this important property depends on the composition and interactions of the constituent macromolecules is poorly understood. Here we use molecular dynamics simulations to determine the interfacial tension and phase equilibrium of model condensate‐forming systems. The model systems consist of binary mixtures of Lennard‐Jones particles or chains of such particles. We refer to the two components as drivers and regulators; the former has stronger self‐interactions and hence a higher critical temperature (Tc) for phase separation. In previous work, we have shown that, depending on the relative strengths of driver‐regulator and driver‐driver interactions, regulators can either promote or suppress phase separation (i.e., increase or decrease Tc). Here we find that the effects of regulators on Tc quantitatively match the effects on interfacial tension (γ). This important finding means that, when a condensate‐forming system experiences a change in macromolecular composition or a change in intermolecular interactions (e.g., by mutation or posttranslational modification, or by variation in solvent conditions such as temperature, pH, or salt), the resulting change in Tc can be used to predict the change in γ and vice versa. We also report initial results showing that disparity in intermolecular interactions drives multiphase coexistence. These findings provide much needed guidance for understanding how biomolecular condensates mediate cellular functions.

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Section: Resultssupporting

confidence: 87%

Macromolecular regulators have matching effects on the phase equilibrium and interfacial tension of biomolecular condensates

Mazarakos

Zhou

2021

Protein Science

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“…This interesting phenomenon has been reported since the early days of theoretical studies of interfacial properties of mixtures [7][8][9][10][11][12][13]. Its presence has been confirmed by different independent theoretical methods for many systems [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27]. The enrichment has caused much attention in the past decades, e.g.…”

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confidence: 86%

“…The focus of the present work is on the investigation of the non-monotonicity of component density profiles ρ i (z) at vapour-liquid interfaces of mixtures. Two similar effects are not covered: the oscillatory layering structure at fluid interfaces (a structural effect which is also observed for pure components) [60][61][62][63] and the non-monotonic behaviour of the total density which is sometimes observed at liquid-liquid and fluidfluid interfaces [27,34,[63][64][65][66][67][68]. The amplitude of the enrichment, i.e.…”

Section: Nanoscopic Interfacial Properties: Enrichment and Relative Adsorptionmentioning

confidence: 97%

“…The literature data is evaluated and the available data on the enrichment is collected in a database that is provided in an electronic form in the Supplementary Material. A comprehensive dataset on the enrichment at vapour-liquid interfaces in simple model mixtures [14,25,27] was used for the training of the model, which is then tested on all available enrichment data. The predictions from that model are practically within the uncertainties of the theory-based computations, which provides a short-cut method to reliably estimate the enrichment from macroscopic properties instead of using complex theoretical methods such as molecular simulations or DGT.…”

mentioning

confidence: 99%

“…The present work is limited to the investigation of vapour-liquid interfaces of binary mixtures of molecular fluids. Related work on electrolyte solutions and ionic liquids [2,[37][38][39][40][41][42][43], on the behaviour of surfactants at interfaces [44][45][46][47][48][49], as well as on the enrichment of components at liquid-liquid interfaces [27,31,33,[50][51][52][53][54] is not covered. Since theoretical methods for the prediction of component density profiles, namely molecular simulation, DGT, and DFT have been reviewed in detail elsewhere [55][56][57][58][59] their description is not subject of the present paper.…”

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confidence: 99%

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Enrichment at vapour–liquid interfaces of mixtures: establishing a link between nanoscopic and macroscopic properties

Stephan

Hasse

2020

International Reviews in Physical Chemistry

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Component density profiles at vapour-liquid interfaces of mixtures can exhibit a non-monotonic behaviour with a maximum that can be many times larger than the densities in the bulk phases. This is called enrichment and is usually only observed for low-boiling components. The enrichment is a nanoscopic property which can presently not be measured experimentally -in contrast to the classical Gibbs adsorption. The available information on the enrichment stems from molecular simulations, density gradient theory, or density functional theory. The enrichment is highly interesting as it is suspected to influence the mass transfer across interfaces. In the present work, we review the literature data and the existing knowledge on this phenomenon and propose an empirical model to establish a link between the nanoscopic enrichment and macroscopic properties -namely vapour-liquid equilibrium data. The model parameters were determined from a fit to a dataset on the enrichment in about 100 binary Lennard-Jones model mixtures that exhibit different types of phase behaviour, which has recently become available. The model is then tested on the entire set of enrichment data that is available in the literature, which includes also mixtures containing nonspherical, polar, and H-bonding components. The model predicts the enrichment data from the literature (2,000 data points) with an AAD of about 16%, which is below the uncertainty of the enrichment data. This establishes a direct link between measurable macroscopic properties and the nanoscopic enrichment and enables predictions of the enrichment at vapour-liquid interfaces from macroscopic data alone.

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Molecular Modeling and Simulation: Model Development, Thermodynamic Properties, Scaling Behavior and Data Management

Heinen

Chatwell

Homes

et al. 2021

High Performance Computing in Science and Engineering '20

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We are outlining our most recent findings, covering: 1) A comparison of a micro-and macroscopic solution of a two-phase Riemann problem obtained from molecular dynamics simulations and finite volume schemes; 2) A novel equation of state for the bulk viscosity of liquid noble gases based on a multi-mode relaxation ansatz; 3) A detailed analysis of the evaporation process of simple fluids; 4) Diffusion coefficients of quaternary liquid mixtures obtained by the Green-Kubo formalism; 5) An analysis of the solid/fluid phase transition for the face centered cubic (fcc) lattice; 6) The relative permittivity of mixtures of water and acetone; 7) An assessment of the reliability and reproducibility of molecular simulation results; 8) Techniques for the data management in simulation workflows, including annotations of simulation outcomes with appropriate metadata standardized by an ontology.

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Interfacial properties of binary mixtures of simple fluids and their relation to the phase diagram

Abstract: Enrichment at vapour–liquid interfaces can be interpreted as a wetting transition in the vicinity of a three phase equilibrium.

Cited by 38 publications

References 122 publications

Macromolecular regulators have matching effects on the phase equilibrium and interfacial tension of biomolecular condensates

Macromolecular regulators have matching effects on the phase equilibrium and interfacial tension of biomolecular condensates

Enrichment at vapour–liquid interfaces of mixtures: establishing a link between nanoscopic and macroscopic properties

Molecular Modeling and Simulation: Model Development, Thermodynamic Properties, Scaling Behavior and Data Management

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