Molecular Characterization of Polymers by ab initio Statistical Mechanics

A methodology of ab initio molecular orbital and statistical mechanics calculations to predict conformational characteristics, crystal conformations, configurational properties, solubilities, crystallization behaviors, and thermal properties of polymers from the primary structure has been developed and applied to polymers that include heteroatoms such as nitrogen, oxygen, silicon, phosphorus, sulfur, and selenium to find a variety of weak attractive interactions due to the heteroatoms. It has also been proved that the weak attractions essentially determine the molecular characteristics of the polymers. The methodology has been improved to include the dependence of conformations of the current and neighboring bonds on geometrical parameters as well as conformational energies and to express the nitrogen inversion for nitrogenous polymers. Herein, the methodology is concisely explained, and actual examples of the conformational and configurational analyses are presented.