Homogeneous nucleation: classical formulas as asymptotic limits of the Cahn-Hilliard approach.
Classical expressions for the critical cluster work of formation approximate the nonclassical expressions based in the density functional theory of capillarity for the limit of low supersaturation degrees. However, the ratio between classical and nonclassical expressions for nucleation rates grows as the supersaturation degree decreases. Here, with the aim to obtain simple and more accurate expressions that approximate the modern nucleation rate formulas, an asymptotic expansion of the Cahn-Hilliard expression of the critical work of formation is developed within the limit of low supersaturation. In such asymptotic expansion, terms up to third order are retained. The ratios between the corrected classical expressions and the nonclassical ones are now decreasing for supersaturation degrees tending to zero. However, the corrected approximate formulas are as difficult to handle as the exact Cahn-Hilliard expressions. When only the two first low-order terms of the asymptotic expansion are retained, a simpler corrected classical expression is obtained but it can only approximate nonclassical expressions up to order unity. Finally, using a Becker-Doring model of nucleation, the kinetic prefactor of the critical nuclei rate of formation is modeled consistently with the Cahn-Hilliard approach to the critical work of formation.
Parra
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E.T.S.I. Aeronáuticos, Universidad Politécnica de Madrid, Plaza Cardenal Cisneros, 3 E28040-Madrid, Spain. ignacio.parra@upm.es
Cordero-Gracia
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Gómez
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D000465:Algorithms; D016000:Cluster Analysis; D007700:Kinetics; D008956:Models, Chemical