The two-phase model for calculating thermodynamic properties of liquids from molecular dynamics: Validation for the phase diagram of Lennard-Jones fluids

Lin, Shiang‐Tai; Blanco, Mario; Goddard, William A.

doi:10.1063/1.1624057

Cited by 486 publications

(718 citation statements)

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“…One method of addressing this issue is the Two-Phase Thermodynamics (2PT) method 1,5 which is based on the Lin, Blanco and Goddard (LBG) theory of condensed phase thermodynamics. The 2PT method builds on an idea first proposed by Eyring and Rae 6 whereby the DoS function of a liquid is expressed as a linear combination of a gas (eqn 5.2) and a solid (eqn 2.3):…”

Section: Aiii Liquids: 2pt Methods For Condensed Phase Systemsmentioning

confidence: 99%

Role of Specific Cations and Water Entropy on the Stability of Branched DNA Motif Structures

et al. 2012

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Section: Aiii Liquids: 2pt Methods For Condensed Phase Systemsmentioning

confidence: 99%

Role of Specific Cations and Water Entropy on the Stability of Branched DNA Motif Structures

et al. 2012

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“…[34]. In that model, the vibrational density of states (DoS) for a liquid is broken into gas-and solid-like contributions, which is conceptually similar to the two-state approach for CAL-PHAD modelling.…”

Section: Glasses and The Glass Transitionmentioning

confidence: 99%

Thermodynamic modelling of liquids: CALPHAD approaches and contributions from statistical physics

Becker

Ågren

Baricco

et al. 2013

Physica Status Solidi (b)

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We describe current approaches to thermodynamic modelling of liquids for the CALPHAD method, the use of available experimental methods and results in this type of modelling, and considerations in the use of atomic-scale simulation methods to inform a CALPHAD approach. We begin with an overview of the formalism currently used in CALPHAD to describe the temperature dependence of the liquid Gibbs free energy and outline opportunities for improvement by reviewing the current physical understanding of the liquid. Brief descriptions of experimental methods for extracting high-temperature data on liquids and the preparation of undercooled liquid samples are presented.Properties of a well-determined substance, B 2 O 3 , including the glass transition, are then discussed in detail to emphasize specific modelling requirements for the liquid. We then examine the two-state model proposed for CALPHAD in detail and compare results with experiment and theory, where available. We further examine the contributions of atomic-scale methods to the understanding of liquids and their potential for supplementing available data. We discuss molecular dynamics (MD) and Monte Carlo methods that employ atomic interactions from classical interatomic potentials, as well as contributions from ab initio MD. We conclude with a summary of our findings.1 Introduction Although few inorganic materials are used in their liquid state, liquids play an important role in the manufacture of many materials. This can be either because they are processed from the liquid or, for fulfilling performance criteria, the formation of the liquid phase must be avoided. Additionally, there are now a number of commercially available amorphous solids, both in the form of oxides and metallic glasses, and accurate descriptions of these sys-tems are necessary over a wide range of temperatures. How-ever, liquid phases of many inorganic substances are only sta-ble at high temperatures where the experimental determination of their properties is more challenging than at lower tem-peratures. Many amorphous phases are, at best, metastable and their properties can be difficult to measure. In addition, the data from glassy phases cannot be directly applied to modelling liquids because they have gone through the glass transition, with the attendant sharp drop in heat capacity. As a result, the experimental data for generating and evaluating models of liquids and glasses are fairly sparse. This has a significant impact on the development and refinement of models that strongly depend on the availability of thermodynamic data, such as those needed in CALPHAD modelling.CALPHAD is one of the major ways to model the thermodynamics of liquids. However, for many systems, especially the unaries (elements and sometimes compounds), the data necessary to develop, parameterize and validate models are limited. Theoretical approaches, e.g. first-principles or classical atomistic simulation, can help provide data

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“…The gas-like contribution is given by the hard sphere (HS) entropy. Using a memory function (MF) formalism, Desjarlais [5] has corrected the short time (high frequency) non-physical behavior of the HS VACF, used originally, while preserving the long time (low frequency) correlation time scale of Lin et al's model [13]. This has resulted in an improved accuracy of the calculated entropies for softer interatomic potentials.…”

Section: Heat Until It Melts (Hum)mentioning

confidence: 99%

“…It utilizes Desjarlais's recent proposal [5] for the calculation of liquid entropy. Desjarlais has enhanced the two-phase thermodynamic (2PT) model of Lin et al [13]. In the 2PT model, the velocity autocorrelation function (VACF) is decomposed into gas-like (diffusive) and solid-like (vibratory) components.…”

Section: Heat Until It Melts (Hum)mentioning

confidence: 99%

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Simple calculation ofab initiomelting curves: Application to aluminum

et al. 2015

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We present a simple, fast, and reliable method to compute the melting curves of materials with ab initio molecular dynamics. It is based on the two-phase thermodynamic model of [Lin et al., J. Chem. Phys. 119, 11792 (2003)] and its improved version given by [Desjarlais, Phys. Rev. E, 88, 062145 (2013)]. In this model, the velocity autocorrelation function is utilized to calculate the contribution of the nuclei motion to the entropy of the solid and liquid phases. It is then possible to find the thermodynamic conditions of equal Gibbs free energy between these phases, defining the melting curve. The first benchmark on the face-centered cubic melting curve of aluminum from 0 to 300 GPa demonstrates how to obtain an accuracy of 5-10%, comparable to the most sophisticated methods, for a much lower computational cost.

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The two-phase model for calculating thermodynamic properties of liquids from molecular dynamics: Validation for the phase diagram of Lennard-Jones fluids

Cited by 486 publications

References 13 publications

Role of Specific Cations and Water Entropy on the Stability of Branched DNA Motif Structures

Role of Specific Cations and Water Entropy on the Stability of Branched DNA Motif Structures

Thermodynamic modelling of liquids: CALPHAD approaches and contributions from statistical physics

Simple calculation ofab initiomelting curves: Application to aluminum

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