Systematic coarse-graining in nucleation theory

M. Schweizer, L.M.C. Sagis

Research output: Contribution to journalArticleAcademicpeer-review

2 Citations (Scopus)

Abstract

In this work, we show that the standard method to obtain nucleation rate-predictions with the aid of atomistic Monte Carlo simulations leads to nucleation rate predictions that deviate 3 - 5 orders of magnitude from the recent brute-force molecular dynamics simulations [Diemand et al., J. Chem. Phys. 139, 074309 (2013)] conducted in the experimental accessible supersaturation regime for Lennard-Jones argon. We argue that this is due to the truncated state space the literature mostly relies on, where the number of atoms in a nucleus is considered the only relevant order parameter. We here formulate the nonequilibrium statistical mechanics of nucleation in an extended state space, where the internal energy and momentum of the nuclei are additionally incorporated. We show that the extended model explains the lack in agreement between the molecular dynamics simulations by Diemand et al. and the truncated state space. We demonstrate additional benefits of using the extended state space; in particular, the definition of a nucleus temperature arises very naturally and can be shown without further approximation to obey the fluctuation law of McGraw and LaViolette. In addition, we illustrate that our theory conveniently allows to extend existing theories to richer sets of order parameters.
Original languageEnglish
Article number074503
Number of pages18
JournalJournal of Chemical Physics
Volume143
DOIs
Publication statusPublished - 2015

Fingerprint

Nucleation
nucleation
Molecular dynamics
nuclei
Statistical mechanics
Argon
Supersaturation
Computer simulation
molecular dynamics
simulation
Momentum
supersaturation
predictions
internal energy
statistical mechanics
Atoms
argon
momentum
approximation
atoms

Keywords

  • vapor-liquid nucleation
  • monte-carlo-simulation
  • translation-rotation paradox
  • homogeneous nucleation
  • molecular-dynamics
  • free-energy
  • supersaturated vapor
  • semiphenomenological theory
  • inhomogeneous-media
  • physical clusters

Cite this

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title = "Systematic coarse-graining in nucleation theory",
abstract = "In this work, we show that the standard method to obtain nucleation rate-predictions with the aid of atomistic Monte Carlo simulations leads to nucleation rate predictions that deviate 3 - 5 orders of magnitude from the recent brute-force molecular dynamics simulations [Diemand et al., J. Chem. Phys. 139, 074309 (2013)] conducted in the experimental accessible supersaturation regime for Lennard-Jones argon. We argue that this is due to the truncated state space the literature mostly relies on, where the number of atoms in a nucleus is considered the only relevant order parameter. We here formulate the nonequilibrium statistical mechanics of nucleation in an extended state space, where the internal energy and momentum of the nuclei are additionally incorporated. We show that the extended model explains the lack in agreement between the molecular dynamics simulations by Diemand et al. and the truncated state space. We demonstrate additional benefits of using the extended state space; in particular, the definition of a nucleus temperature arises very naturally and can be shown without further approximation to obey the fluctuation law of McGraw and LaViolette. In addition, we illustrate that our theory conveniently allows to extend existing theories to richer sets of order parameters.",
keywords = "vapor-liquid nucleation, monte-carlo-simulation, translation-rotation paradox, homogeneous nucleation, molecular-dynamics, free-energy, supersaturated vapor, semiphenomenological theory, inhomogeneous-media, physical clusters",
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doi = "10.1063/1.4927338",
language = "English",
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journal = "Journal of Chemical Physics",
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Systematic coarse-graining in nucleation theory. / Schweizer, M.; Sagis, L.M.C.

In: Journal of Chemical Physics, Vol. 143, 074503, 2015.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Systematic coarse-graining in nucleation theory

AU - Schweizer, M.

AU - Sagis, L.M.C.

PY - 2015

Y1 - 2015

N2 - In this work, we show that the standard method to obtain nucleation rate-predictions with the aid of atomistic Monte Carlo simulations leads to nucleation rate predictions that deviate 3 - 5 orders of magnitude from the recent brute-force molecular dynamics simulations [Diemand et al., J. Chem. Phys. 139, 074309 (2013)] conducted in the experimental accessible supersaturation regime for Lennard-Jones argon. We argue that this is due to the truncated state space the literature mostly relies on, where the number of atoms in a nucleus is considered the only relevant order parameter. We here formulate the nonequilibrium statistical mechanics of nucleation in an extended state space, where the internal energy and momentum of the nuclei are additionally incorporated. We show that the extended model explains the lack in agreement between the molecular dynamics simulations by Diemand et al. and the truncated state space. We demonstrate additional benefits of using the extended state space; in particular, the definition of a nucleus temperature arises very naturally and can be shown without further approximation to obey the fluctuation law of McGraw and LaViolette. In addition, we illustrate that our theory conveniently allows to extend existing theories to richer sets of order parameters.

AB - In this work, we show that the standard method to obtain nucleation rate-predictions with the aid of atomistic Monte Carlo simulations leads to nucleation rate predictions that deviate 3 - 5 orders of magnitude from the recent brute-force molecular dynamics simulations [Diemand et al., J. Chem. Phys. 139, 074309 (2013)] conducted in the experimental accessible supersaturation regime for Lennard-Jones argon. We argue that this is due to the truncated state space the literature mostly relies on, where the number of atoms in a nucleus is considered the only relevant order parameter. We here formulate the nonequilibrium statistical mechanics of nucleation in an extended state space, where the internal energy and momentum of the nuclei are additionally incorporated. We show that the extended model explains the lack in agreement between the molecular dynamics simulations by Diemand et al. and the truncated state space. We demonstrate additional benefits of using the extended state space; in particular, the definition of a nucleus temperature arises very naturally and can be shown without further approximation to obey the fluctuation law of McGraw and LaViolette. In addition, we illustrate that our theory conveniently allows to extend existing theories to richer sets of order parameters.

KW - vapor-liquid nucleation

KW - monte-carlo-simulation

KW - translation-rotation paradox

KW - homogeneous nucleation

KW - molecular-dynamics

KW - free-energy

KW - supersaturated vapor

KW - semiphenomenological theory

KW - inhomogeneous-media

KW - physical clusters

U2 - 10.1063/1.4927338

DO - 10.1063/1.4927338

M3 - Article

VL - 143

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

M1 - 074503

ER -