Effect of Confinement and Heterogeneity on Phase Behavior: A Density Functional Approach

• Main Author: Husowitz, Barry Charles
• Other Authors: Talanquer, Vicente A.
• Language: en
• Published: The University of Arizona. 2007
• Subjects: DFT; Nucleation; Statistical Mechanics
• Online Access: http://hdl.handle.net/10150/196124

Density functional theory of statistical mechanics in a square gradient approximation was used to study nucleation in confined systems such as a cylindrical pore and in-between two cylindrical disks. This approximation was further applied to study the evaporation and condensation in nanopores with finite lengths. Confinement effects induced nucleation phenomena that are not observed in more open systems. Density functional theory was also used to explore the solvation properties of a spherical solute immersed in a supercritical diatomic fluid. The solute was modeled as a hard core Yukawa particle surrounded by a diatomic Lennard-Jones fluid represented by two fused tangent spheres using an interaction site approximation. The results of this study indicate that local density augmentation and the solvation free energies are particularly sensitive to changes in solute and solvent particle geometry and solute/solvent anisotropic interactions. Density functional theory allowed us to systematically study the effect of a variety of geometric and interaction parameters on the properties and behavior of all the systems. Although more sophisticated, but computationally more demanding, theoretical approaches can be used, our results provide fundamental physical insights into the behavior of real systems and create a solid basis for the development of more realistic models.