What is "liquid"? Understanding the states of matter

Barker, John A.; Henderson, Douglas

doi:10.1103/revmodphys.48.587

Cited by 2,085 publications

(1,096 citation statements)

References 541 publications

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“…To do so, we first determine an effective hard-sphere ion diameter from the WCA potentials that we have assumed. Barker et al 33,42 match the configurational partition function for a system of particles with an arbitrary pairwise potential to a reference system of hard-spheres; they prescribe an effective hard-sphere diameter σ eff from the WCA diameter σ…”

Section: Methodsmentioning

confidence: 99%

“…More accurate models for excluded volume contributions to the bulk chemical potential frequently rely on integral equation expansions of a homogeneous hard-sphere fluid. 32,33 The Carnahan−Starling (CS) equation of state 27 is an accurate approximation 34 that combines the hard-sphere equations of state from the virial and compressibility routes 35 to obtain …”

Section: Electric Double-layer Modelsmentioning

confidence: 99%

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Electric Double-Layer Structure in Primitive Model Electrolytes: Comparing Molecular Dynamics with Local-Density Approximations

et al. 2015

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ABSTRACT:We evaluate the accuracy of local-density approximations (LDAs) using explicit molecular dynamics simulations of binary electrolytes comprised of equisized ions in an implicit solvent. The Bikerman LDA, which considers ions to occupy a lattice, poorly captures excluded volume interactions between primitive model ions. Instead, LDAs based on the Carnahan− Starling (CS) hard-sphere equation of state capture simulated values of ideal and excess chemical potential profiles extremely well, as well as the relationship between surface charge density and electrostatic potential. Excellent agreement between the EDL capacitances predicted by CS-LDAs and computed in molecular simulations is found even in systems where ion correlations drive strong density and free charge oscillations within the EDL, despite the inability of LDAs to capture the oscillations in the detailed EDL profiles.

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Section: Methodsmentioning

confidence: 99%

Section: Electric Double-layer Modelsmentioning

confidence: 99%

Electric Double-Layer Structure in Primitive Model Electrolytes: Comparing Molecular Dynamics with Local-Density Approximations

et al. 2015

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“…Moreover, hard-sphere models are commonly used as a reference systems for perturbation approaches to the statistical mechanics of interacting particle systems [19,38,39]. In fact, the idea of representing a liquid by a system of hard bodies can be already found in the work of Van der Waals: his famous equation of state was derived using essentially this principle.…”

Section: Model and Simulation Detailsmentioning

confidence: 99%

Probing local equilibrium in nonequilibrium fluids

2015

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We use extensive computer simulations to probe local thermodynamic equilibrium (LTE) in a quintessential model fluid, the two-dimensional hard-disks system. We show that macroscopic LTE is a property much stronger than previously anticipated, even in the presence of important finite size effects, revealing a remarkable bulk-boundary decoupling phenomenon in fluids out of equilibrium. This allows us to measure the fluid's equation of state in simulations far from equilibrium, with an excellent accuracy comparable to the best equilibrium simulations. Subtle corrections to LTE are found in the fluctuations of the total energy which strongly point out to the nonlocality of the nonequilibrium potential governing the fluid's macroscopic behavior out of equilibrium.

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“…This is consistent with the van der Waalsian picture of fluids where the hard molecular core is treated as a reference which determines the fluid structure, while the dispersions (attractions) are incorporated as a perturbation. [68][69][70] A simple hard-core model which also includes attractive interactions would certainly be appropriate to investigate the phase diagrams of thermotropic LCs. A number of studies have been carried out after the early attempts by Kimura 71 to describe the properties of a system which combines Onsager's hard-rod model with anisotropic dispersion forces.…”

Section: Introductionmentioning

confidence: 99%

Understanding and Describing the Liquid-Crystalline States of Polypeptide Solutions: A Coarse-Grained Model of PBLG in DMF

Müller

Jackson

2014

Macromolecules

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A perturbation theory is employed to construct a free-energy functional capable of describing the isotropic and nematic phases of attractive rod-like particles. An algebraic van der Waals-Onsager equation of state is then developed to determine the global phase behaviour of prolate particles for various aspect ratios and strengths of the attractive potential. Compared with the phase diagram of their athermal analogues, the incorporation of an attractive potential is seen to stabilize the nematic state leading to an increase in the degree of orientational order of the system at high densities. The most salient feature of these fluids is the existence of regions of nematic-nematic phase separation. The simple model is used to describe the phase behaviour of solutions of a relatively rigid polypeptide, poly-(γ -benzyl-L-glutamate) (PBLG), in dimethylformamide (DMF); this system exhibits a unique phase separation between two liquidcrystalline states. The coarse-grained representation of the mesogen employed herein * To whom correspondence should be addressed 1 is a hard spherocylinder decorated with an attractive square-well potential which acts at the center of mass of the particle. A quantitative description of the experimental isotropic-nematic phase behaviour of the PBLG solutions can be achieved from the proposed model with the use of just two temperature-dependent parameters.

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What is "liquid"? Understanding the states of matter

Cited by 2,085 publications

References 541 publications

Electric Double-Layer Structure in Primitive Model Electrolytes: Comparing Molecular Dynamics with Local-Density Approximations

Electric Double-Layer Structure in Primitive Model Electrolytes: Comparing Molecular Dynamics with Local-Density Approximations

Probing local equilibrium in nonequilibrium fluids

Understanding and Describing the Liquid-Crystalline States of Polypeptide Solutions: A Coarse-Grained Model of PBLG in DMF

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