Homogeneous nucleation processes are characterized by the nucleation rate and the critical droplet size. Molecular dynamics simulation is applied for studying homogeneous nucleation during condensation of supersaturated vapors of methane and ethane. The results are compared with the classical nucleation theory (CNT) and the Laaksonen–Ford–Kulmala (LFK) model that introduces the size dependence of the specific surface energy. It is shown for the nucleation rate that the Yasuoka–Matsumoto method and the mean first passage time method lead to considerably differing results. Even more significant deviations are found between two other approaches to the critical droplet size, based on the maximum of the Gibbs free energy of droplet formation (Yasuoka–Matsumoto) and the supersaturation dependence of the nucleation rate (nucleation theorem). CNT is found to agree reasonably well with the simulation results, whereas LFK leads to large deviations at high temperatures.
Issue Section:
Micro/Nanoscale Heat Transfer—Part Ii
Keywords:
condensation,
drops,
free energy,
molecular dynamics method,
nucleation,
organic compounds,
surface energy,
phase transition,
nucleation,
molecular dynamics
Topics:
Drops,
Methane,
Nucleation (Physics),
Surface energy,
Vapors,
Simulation,
Molecular dynamics
1.
Lee
, S. -H.
, Reeves
, J. M.
, Wilson
, J. C.
, Hunton
, D. E.
, Viggiano
, A. A.
, Miller
, T. M.
, Ballenthin
, J. O.
, and Lait
, L. R.
, 2003, “Particle Formation by Ion Nucleation in the Upper Troposphere and Lower Stratosphere
,” Science
0036-8075, 301
, pp. 1886
–1889
.2.
Määttänen
, A.
, Vehkamäki
, H.
, Lauri
, A.
, Merikallio
, S.
, Kauhanen
, J.
, Savijärvi
, H.
, and Kulmala
, M.
, 2005, “Nucleation Studies in the Martian Atmosphere
,” J. Geophys. Res.
0148-0227, 110
, p. E02002
.3.
Curtius
, J.
, 2006, “Nucleation of Atmospheric Aerosol Particles
,” C. R. Phys.
, 7
, pp. 1027
–1045
. 1631-07054.
Volmer
, M.
, and Weber
, A.
, 1926, “Keimbildung in übersättigten Gebilden
,” Z. Phys. Chem. (Leipzig)
, 119
, pp. 277
–301
. 0323-44795.
Feder
, J.
, Russell
, K. C.
, Lothe
, J.
, and Pound
, G. M.
, 1966, “Homogeneous Nucleation and Growth of Droplets in Vapours
,” Adv. Phys.
0001-8732, 15
(1
), pp. 111
–178
.6.
Laaksonen
, A.
, Ford
, I. J.
, and Kulmala
, M.
, 1994, “Revised Parametrization of the Dillmann–Meier Theory of Homogeneous Nucleation
,” Phys. Rev. E
1063-651X, 49
(6
), pp. 5517
–5524
.7.
Tanaka
, K. K.
, Kawamura
, K.
, Tanaka
, H.
, and Nakazawa
, K.
, 2005, “Tests of the Homogeneous Nucleation Theory With Molecular-Dynamics Simulations
,” J. Chem. Phys.
0021-9606, 122
, p. 184514
.8.
Tolman
, R. C.
, 1949, “The Effect of Droplet Size on Surface Tension
,” J. Chem. Phys.
0021-9606, 17
(3
), pp. 333
–337
.9.
Kirkwood
, J. G.
, and Buff
, F. P.
, 1949, “The Statistical Mechanical Theory of Surface Tension
,” J. Chem. Phys.
0021-9606, 17
(3
), pp. 338
–343
.10.
Vrabec
, J.
, Kedia
, G. K.
, Fuchs
, G.
, and Hasse
, H.
, 2006, “Comprehensive Study on Vapour-Liquid Coexistence of the Truncated and Shifted Lennard–Jones Fluid Including Planar and Spherical Interface Properties
,” Mol. Phys.
0026-8976, 104
(9
), pp. 1509
–1527
.11.
Napari
, I.
, and Laaksonen
, A.
, 2007, “Surface Tension and Scaling of Critical Nuclei in Diatomic and Triatomic Fluids
,” J. Chem. Phys.
0021-9606, 126
, p. 134503
.12.
Yasuoka
, K.
, and Matsumoto
, M.
, 1998, “Molecular Dynamics of Homogeneous Nucleation in the Vapor Phase
,” J. Chem. Phys.
0021-9606, 109
(19
), pp. 8451
–8470
.13.
Haber
, F.
, 1922, “Über amorphe Niederschläge und krystallisierte Sole
,” Ber. Dtsch. Chem. Ges. B
0365-9488, 55
, pp. 1717
–1733
.14.
Matsubara
, H.
, Koishi
, T.
, Ebisuzaki
, T.
, and Yasuoka
, K.
, 2007, “Extended Study of Molecular Dynamics Simulation of Homogeneous Vapor-Liquid Nucleation of Water
,” J. Chem. Phys.
0021-9606, 127
, p. 214507
.15.
Nellas
, R. B.
, Chen
, B.
, and Siepmann
, J. I.
, 2007, “Dumbbells and Onions in Ternary Nucleation
,” Phys. Chem. Chem. Phys.
, 9
, pp. 2779
–2781
. 1463-907616.
Wedekind
, J.
, Reguera
, D.
, and Strey
, R.
, 2006, “Finite-Size Effects in Simulation of Nucleation
,” J. Chem. Phys.
0021-9606, 125
, p. 214505
.17.
Horsch
, M.
, Vrabec
, J.
, Bernreuther
, M.
, Grottel
, S.
, Reina
, G.
, Wix
, A.
, Schaber
, K.
, and Hasse
, H.
, 2008, “Homogeneous Nucleation in Supersaturated Vapors of Methane, Ethane, and Carbon Dioxide Predicted by Brute Force Molecular Dynamics
,” J. Chem. Phys.
0021-9606, 128
, p. 164510
.18.
Römer
, F.
, and Kraska
, T.
, 2007, “Homogeneous Nucleation and Growth in Supersaturated Zinc Vapor Investigated by Molecular Dynamics Simulation
,” J. Chem. Phys.
0021-9606, 127
, p. 234509
.19.
Oxtoby
, D. W.
, and Kashchiev
, D.
, 1994, “A General Relation Between the Nucleation Work and the Size of the Nucleus in Multicomponent Nucleation
,” J. Chem. Phys.
0021-9606, 100
(10
), pp. 7665
–7671
.20.
Linhart
, A.
, Chen
, C.
, Vrabec
, J.
, and Hasse
, H.
, 2005, “Thermal Properties of the Metastable Supersaturated Vapor of the Lennard–Jones Fluid
,” J. Chem. Phys.
0021-9606, 122
, p. 144506
.21.
Nie
, C.
, Geng
, J.
, and Marlow
, W. H.
, 2008, “Study of Thermal Properties of the Metastable Supersaturated Vapor With the Restricted Ensemble
,” Physica A
, 387
, pp. 1433
–1438
. 0378-437122.
Baidakov
, V. G.
, Protsenko
, S. P.
, and Kozlova
, Z. R.
, 2008, “Thermal and Caloric Equations of State for Stable and Metastable Lennard-Jones Fluids: I. Molecular-dynamics Simulations
,” Fluid Phase Equilib.
, 263
, pp. 55
–63
. 0378-381223.
Vrabec
, J.
, Stoll
, J.
, and Hasse
, H.
, 2001, “A Set of Molecular Models for Symmetric Quadrupolar Fluids
,” J. Phys. Chem. B
1089-5647, 105
(48
), pp. 12126
–12133
.24.
Trokhymchuk
, A.
, and Alejandre
, J.
, 1999, “Computer Simulations of Liquid/Vapor Interface in Lennard–Jones Fluids: Some Questions and Answers
,” J. Chem. Phys.
0021-9606, 111
(18
), pp. 8510
–8523
.25.
Shen
, V. K.
, Mountain
, R. D.
, and Errington
, J. R.
, 2007, “Comparative Study of the Effect of Tail Corrections of Surface Tension Determined by Molecular Simulation
,” J. Phys. Chem. B
1089-5647, 111
(22
), pp. 6198
–6207
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