Conformational Theory of Large Molecules

Over the quarter century since the publication of Flory's classic Statistical Mechanics of Chain Molecules, the rotational isomeric state model for averaging conformation-dependent properties of macromolecules has become a popular tool of polymer chemists, and it has been improved and refined in numerous important ways. Formulations for the quantitative description of several properties have been simplified and generalized, new formulations for the treatment of additional properties have been created, and there has been an explosion of applications to different polymers. A growing number of chemists who synthesize polymers and copolymers from monomer units of increasing complexity look to rotational isomeric state theory as the only model that describes the properties of the macromolecule in terms of the real covalent structure in a computationally efficient manner. Ubiquitous computers, coupled with software packages for the visualization and manipulation of atom-based polymer models, also contribute to increased use of the technique. Conformational Theory of Large Molecules is a successor to Flory's landmark monograph. It both describes the current status of rotational isomeric state theory and explains how the calculations can be performed. The book's fifteen chapters are conceptually arranged into four groups: The first two chapters introduce material for the theoretical description of chain molecules and the experimental observables that are most frequently addressed by rotational isomeric state methods. The second group consists of four chapters that develop the rotational isomeric state model, from simple alkanes. Group three expands the scope of polymer types that can be treatedwith this model, and the book's final three chapters expand the scope of conformation-dependent physical properties that can be so treated. For students and professional chemists who want to perform rotational isomeric state calculations for particular polymers, 174 end-of-chapter problems serve to clarify difficult points - 70% of the problems are answered in an appendix. A FORTRAN program is included to perform calculations for the most important property of regular polymers, the characteristic ratio (mean square unperturbed end-to-end distance).