Density Functional Theory of Inhomogeneous Liquids IV. Squared-gradient approximation and Classical Nucleation Theory
arXiv:1104.3410 · doi:10.1063/1.3582901
Abstract
The Squared-Gradient approximation to the Modified-Core Van der Waals density functional theory model is developed. A simple, explicit expression for the SGA coefficient involving only the bulk equation of state and the interaction potential is given. The model is solved for planar interfaces and spherical clusters and is shown to be quantitatively accurate in comparisons to computer simulations. An approximate technique for solving the SGA based on piecewise-linear density profiles is introduced and is shown to give reasonable zeroth-order approximations to the numerical solution of the model. The piecewise-linear models of spherical clusters are shown to be a natural extension of Classical Nucleation Theory and serve to clarify some of the non-classical effects previously observed in liquid-vapor nucleation. Nucleation pathways are investigated using both constrained energy-minimization and steepest-descent techniques.
to appear in J. Chem. Phys
References in corpus (8)
- Reversible Work Transiton State Theory: Application to Dissociative Adsorption of Hydrogen
- Dependence of the liquid-vapor surface tension on the range of interaction: a test of the law of corresponding states
- Density Functional Theory of Inhomogeneous Liquids: III. Liquid-Vapor Nucleation
- Density Functional Theory of Inhomogeneous Liquids: II. A Fundamental Measure Approach
- Theoretical description of the nucleation of vapor bubbles in a superheated fluid
- Density functional theory of inhomogeneous liquids. I. The liquid-vapor interface in Lennard-Jones fluids
- First Principles Derivation of Effective Ginzburg-Landau Free Energy models for Crystalline Systems
- Phase behavior of a confined nano-droplet in the grand-canonical ensemble: the reverse liquid-vapor transition
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