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Journal ArticleDOI

Gibbs-Duhem integration: a new method for direct evaluation of phase coexistence by molecular simulation

David A. Kofke
- 20 Apr 1993 - 
- Vol. 78, Iss: 6, pp 1331-1336
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TLDR
In this article, a method that combines the best elements of thermodynamic integration and the Gibbs ensemble technique is proposed for the direct evaluation of phase equilibria by molecular simulation, given the conditions of coexistence at a single state point, simultaneous but independent NPT simulations of each phase are performed in succession along the saturation line.
Abstract
A method that combines the best elements of thermodynamic integration and the Gibbs ensemble technique is proposed for the direct evaluation of phase equilibria by molecular simulation. Given the conditions of coexistence at a single state point, simultaneous but independent NPT simulations of each phase are performed in succession along the saturation line. In each simulation, the pressure is adjusted to satisfy chemical potential equality according to the Gibbs-Duhem equation. Each coexistence point is determined by just one simulation, and particle insertions are never performed or attempted. Vapourliquid coexistence for the Lennard-Jones model is evaluated, and extensions are discussed.

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Citations
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Gibbs Ensemble and Histogram Reweighting Grand Canonical Monte Carlo Methods

TL;DR: The focus of the present chapter is on simulations of phase equilibrium properties of fluids and classical force-field-based simulations start by postulating a functional form for the phase behavior of fluids.
Journal ArticleDOI

Inverse melting in a two-dimensional off-lattice model

TL;DR: In this article, the authors carried out computer simulations of a simple, two-dimensional off-lattice model that exhibits inverse melting, where core-softened disks interacting through a repulsive square shoulder located inside an attractive square well.
Journal ArticleDOI

Freezing Transition Studies Through Constrained Cell Model Simulation

TL;DR: A simulation method based on cell models is used to deduce the fluid–solid transition of a system of particles that interact via a pair potential, and the phase diagram of the corresponding constrained cell model is found to contain both a stable critical point and a triple point.
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Long-range behaviour in liquid crystals by computer simulation

TL;DR: In this article, a review of recent work in which simulations have been used to study bulk liquid crystalline phase diagrams, large-scale fluctuations near phase transitions, and elastic deformation near surfaces, making links with the appropriate theories.
References
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Book

Computer Simulation of Liquids

TL;DR: In this paper, the gear predictor -corrector is used to calculate forces and torques in a non-equilibrium molecular dynamics simulation using Monte Carlo methods. But it is not suitable for the gear prediction problem.
Journal ArticleDOI

Direct determination of phase coexistence properties of fluids by Monte Carlo simulation in a new ensemble

TL;DR: In this article, a methodology is presented for Monte Carlo simulation of fluids in a new ensemble that can be used to obtain phase coexistence properties of multicomponent systems from a single computer experiment.
Journal ArticleDOI

Phase equilibria by simulation in the Gibbs ensemble

TL;DR: In this article, the Gibbs-ensemble Monte Carlo simulation methodology for phase equilibrium calculations proposed by Panagiotopoulos is generalized and applied to mixture and membrane equilibria, and an alternative derivation of the Gibbs simulation criteria based on the limiting distributions for the appropriate statistical mechanical ensembles is presented.
Journal ArticleDOI

Direct Determination of Fluid Phase Equilibria by Simulation in the Gibbs Ensemble: A Review

TL;DR: Gibbs Ensemble Monte Carlo (GEMC) as mentioned in this paper is a widely used Monte Carlo method for direct determination of phase coexistence in fluids, which requires only a single simulation per coexistence point.