Lattice model of linear telechelic polymer melts. I. Inclusion of chain semiflexibility in the lattice cluster theory

TL;DR

This paper extends the lattice cluster theory to include chain semiflexibility in linear telechelic polymer melts, enabling analysis of how chain stiffness affects thermodynamics and glass formation in self-assembling polymers.

Contribution

The authors introduce a bending energy penalty into the lattice cluster theory to model chain semiflexibility in telechelic polymers, deriving an analytical free energy expression.

Findings

Provides a theoretical framework for chain stiffness effects

Enables study of self-assembly influence on glass transition

Facilitates exploration of thermodynamics in semiflexible polymers

Abstract

The lattice cluster theory (LCT) for the thermodynamics of polymer systems has recently been reformulated to treat strongly interacting self-assembling polymers composed of fully flexible linear telechelic chains [J. Dudowicz and K. F. Freed, J. Chem. Phys. \textbf{136}, 064902 (2012)]. Here, we further extend the LCT for linear telechelic polymer melts to include a description of chain semiflexibility, which is treated by introducing a bending energy penalty whenever a pair of consecutive bonds from a single chain lies along orthogonal directions. An analytical expression for the Helmholtz free energy is derived for the model of semiflexible linear telechelic polymer melts. The extension provides a theoretical tool for investigating the influence of chain stiffness on the thermodynamics of self-assembling telechelic polymers, and for further exploring the influence of self-assembly on glass formation in such systems.