Insights into Associating Fluid Properties and Microstructure from Classical Density Functional Theory

Self-assembly, important in industrial and biological processes, is governed not only by molecular size and shape, but also by hydrogen bonding forces and hydrophobicities, both of which have important temperature-dependent consequences. Recent advances in statistical mechanics enable the study of these processes at the molecular level. We discuss one such approach based on classical density functional theory. The theory, based on extensions and simplifications of Wertheim’s theory for associating molecules, is applicable to study the behavior of water at hydrophobic and hydrophilic surfaces and supramolecular assembly based on intermolecular association of polyatomic molecules. Insights into the theory and into the physics of associating molecules are discussed.