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Molecular modeling of polymers: I. Correct and efficient enumeration of intrachain conformational energetics
Author(s) -
Orchard B. J.,
Tripathy S. K.,
Pearlstein R. A.,
Hopfinger A. J.
Publication year - 1987
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540080104
Subject(s) - intramolecular force , energetics , chain (unit) , polymer , degrees of freedom (physics and chemistry) , tacticity , chemistry , computational chemistry , chemical physics , thermodynamics , physics , stereochemistry , quantum mechanics , organic chemistry , polymerization
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 chain 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.