Pure and Applied Chemistry

Abstract: At liquid-like densities, molecules of complex fluids can assume a variety of structures (or positions) in space; when the molecules contain many atoms as, for example, in polymers, that variety becomes very large. Further, when confined to a narrow space, it is possible to achieve structures that are not normally observed. Thanks to recent advances in statistical mechanics and molecular physics, and thanks to increasingly fast computers, it is now possible to calculate a fluid's structure, that is, the positions of molecules at equilibrium under given conditions. Calculation of fluid structure is useful because thermodynamic properties depend strongly on that structure, leading to possible applications for new materials. Three examples illustrate some recent developments; each example is presented only schematically (with a minimum of equations) to indicate the physical basis of the mathematical description. The first example considers the effect of branching on self-assembly (micellization) of copolymers (with possible long-range applications in medicine). The second and third examples consider the effect of confinement on fluid structure: first, crystallization in a narrow, confined space to produce a desired crystal structure (with possible applications for light-emitting diodes) and second, suppression of micellization of a diblock copolymer in a thin film (with possible application in lithography). Whenever possible, theoretical calculations are compared with experimental results.