Abstract
The spacio—geotnetric characteristics of macromolecular chains are discussed from the point of view of the essential connections they provide between chemical constitution and properties. Quantities such as molecular weight, radius of gyration, degree of branching, etc., that characterize the molecule as a whole do not suffice for an understanding of the virtually endless variations in the properties that distinguish one polymer from another. For this purpose it is necessary to examine the chemical structures of the constituent units, taking into account the geometric parameters pertaining to chemical bonds, the conformations accessible to the chain skeleton and the resulting spatial configurations. The physical principles underlying the statistical mechanical treatment of conformations of long chain molecules and of their configuration—dependent properties are summarized. Correlations between bonds of the chain and the range of such correlations provide insights into the spatial characteristics of polymer chains. Persistences expressing the configurational averages of vectors spanning sequences of chain units are particularly useful in this connection. Experimental methods that provide quantitative information on conformation and the correlations between units of the chain are briefly discussed.
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