Criteria for validity of thermodynamic equations from non-equilibrium molecular dynamics simulations

Kjelstrup, Signe; Bedeaux, Dick; Inzoli, Isabella; Simon, Jean-Marc

doi:10.1016/j.energy.2008.04.005

Cited by 41 publications

(28 citation statements)

References 56 publications

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“…We note that our simulations are significantly more precise than previous works on nonequilibrium vapor-liquid systems [31,39]. High-precision was required to discern small gauge changes and was achieved by two means.…”

Section: Nonequilibrium Systemsmentioning

confidence: 94%

Nonequilibrium thermodynamics of an interface

2016

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Interfacial thermodynamics has deep ramifications in understanding the boundary conditions of transport theories. We present a formulation of local equilibrium for interfaces that extends the thermodynamics of the "dividing surface," as introduced by Gibbs, to nonequilibrium settings such as evaporation or condensation. By identifying the precise position of the dividing surface in the interfacial region with a gauge degree of freedom, we exploit gauge-invariance requirements to consistently define the intensive variables for the interface. The model is verified under stringent conditions by employing high-precision nonequilibrium molecular-dynamics simulations of a coexisting vapor-liquid Lennard-Jones fluid. We conclude that the interfacial temperature is determined using the surface tension as a "thermometer," and it can be significantly different from the temperatures of the adjacent phases. Our findings lay foundations for nonequilibrium interfacial thermodynamics.

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Section: Nonequilibrium Systemsmentioning

confidence: 94%

Nonequilibrium thermodynamics of an interface

2016

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“…9). From an experimental point of view (Eames 1997;Bedeaux and Kjelstrup 1999;Fang 1999;Marek and Straub 2001) or using molecular dynamics numerical simulation (Matsumoto 1998;Meland et al 2003;Kjelstrup et al 2008), a large amount of research has been done to test the validity of this law, and to evaluate the weighting coefficient, . So far, the influence of adsorptive forces has not been investigated, although they can significantly modify the physical properties of water (Skipper 1998;Park and Sposito 2002;Porion et al 2007).…”

Section: Introductionmentioning

confidence: 99%

Water Evaporation Versus Condensation in a Hygroscopic Soil

2009

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The liquid/vapour phase change of water in soil is involved in many environmental geotechnical processes. In the case of hygroscopic soils, the liquid water is strongly adsorbed on the solid phase and this particular thermodynamic state can highly influence the phase change kinetics. Based on the linear Thermodynamic of Irreversible Processes ideas, the non-equilibrium phase change rate is written as a linear function of the water chemical potential difference between the liquid and vapour state. In this relation, the system is characterized by a phenomenological coefficient that depends on the state variables. Using an original experimental set-up able to analyze the response of a porous medium subjected to non-equilibrium conditions, the phase change coefficient is determined in various configurations. This paper focuses on the influence of the gas phase pressure and underlines that a low gas pressure decreases the phase change kinetics. Then, evaporation and condensation processes are compared showing an asymmetric behaviour. These experimental results are interpreted from a microscopic point of view by relying on recent works dealing with molecular dynamics numerical simulation of the liquid/gas interface.

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“…The original result has been extended to many different cases and it is now a whole new theoretical framework which encompasses the previous linear response theory and goes beyond that, to include far from equilibrium phenomena, such as turbulence and the dynamics of granular materials [32]. In spite of these exciting achievements, the formulation of a mesoscopic non-equilibrium thermodynamics theory able to analyze irreversible processes at very small scales is still problematic [34,35]. The theory of small-system thermodynamics was developed by Hill [36], mainly dealing with isolated nanoparticles, and, even though it has been successfully applied since then [37], a universal framework is still out of sight.…”

Section: Introductionmentioning

confidence: 99%

The notion of energy through multiple scales: From a molecular level to fluid flows and beyond

Asinari

Chiavazzo

2014

Energy

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In the present paper, we review the consistent definition of macroscopic total energy in classical fluid mechanics, as a function of the microscopic canonical Hamiltonian field, based on a Lennard-Jones model with some spatially varying external field. The macroscopic total energy (sum of mechanical and internal energy) is proved to be equal to the equilibrium ensemble-averaged Hamiltonian. In particular, the conditions for including the effects of the external field both in the macroscopic potential energy and in the internal energy are discussed. We present the notion of energy as defined in different scientific communities, starting from the standard macroscopic systems all the way down to small ones, which are gaining an increasing popularity.

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Criteria for validity of thermodynamic equations from non-equilibrium molecular dynamics simulations

Cited by 41 publications

References 56 publications

Nonequilibrium thermodynamics of an interface

Nonequilibrium thermodynamics of an interface

Water Evaporation Versus Condensation in a Hygroscopic Soil

The notion of energy through multiple scales: From a molecular level to fluid flows and beyond

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