Molecular modeling of polymers: I. Correct and efficient enumeration of intrachain conformational energetics

✍ Scribed by B. J. Orchard; S. K. Tripathy; R. A. Pearlstein; A. J. Hopfinger

• Publisher: John Wiley and Sons
• Year: 1987
• Tongue: English
• Weight: 980 KB
• Volume: 8
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.540080104

✦ Synopsis

Polymer conformational analyses can require being able to model the intramolecular energetics of a very long (infinite) chain employing calculations carried out on a relatively short cham sequence. A method to meet this need, based upon symmetry considerations and molecular mechanics energetics, has been developed. Given N equivalent degrees of freedom in a linear polymer chain, N unique molecular groups are determined within the chain. A molecular unit is defined as a group of atoms containing backbone rotational degrees of conformational freedom on each of its ends. The interaction of these N molecular groups, each with a finite number of nearest neighbors, properly describe the intramolecular energetics of a long (infinite) polymer chain. Thus, conformational energetics arising from arbitrarily distant neighbor interactions can be included in the estimation of statistical and thermodynamic properties of a linear polymeric system. This approach is called the polymer reduced interaction matrix method (PRIMM) and the results of applying it to isotactic polystyrene (I-PS) are presented by way of example.