Recent advances in classical density functional theory for associating and polyatomic molecules

The function and stability of macromolecular systems, important in industrial and biological processes, are governed not only by molecular size and shape, but also by temperature-dependent hydrogen bonding forces and hydrophobicity of the system. Such processes can be found in many facets of chemistry and biology, most notably in self-assembly processes such as the formation of membranes and micelles in liquid or surfactant solutions, structuring in polymer/nanoparticle systems and the folding of proteins into stable, functional complexes.We explore the range of capabilities to model such systems through classical density functional theory. Examples demonstrate capabilities of providing molecular insight into properties and structure of branched copolymer/nanoparticle systems, surfactant systems, and grafted polymers. Further opportunities to extend the theories to supramolecular assemblies and to create hybrid approaches with molecular simulation are discussed.

Research highlights
► A thorough review of classical density functional theory and its history.
► Outline basic concepts emphasizing Wertheim's first-order perturbation theory.
► Demonstrate capability with analysis of applications to array of complex systems.
► Indicate multiple directions for necessary future developments of the field.
► Applications include surfactants, lipids, nanocomposites, and tethered polymers.