A perturbation density functional theory for the competition between inter and intramolecular association

TL;DR

This paper introduces a novel density functional theory incorporating intramolecular association in chain molecules, validated by Monte Carlo simulations, revealing significant effects on interfacial properties.

Contribution

It develops the first density functional theory that explicitly accounts for intramolecular association in chain molecules, extending Wertheim's thermodynamic perturbation framework.

Findings

Theory and simulations agree well

Intramolecular association affects interfacial tension

Partition coefficient is significantly influenced

Abstract

Using the framework of Wertheim's thermodynamic perturbation theory we develop the first density functional theory which accounts for intramolecular association in chain molecules. To test the theory new Monte Carlo simulations are performed at a fluid solid interface for a 4 segment chain which can both intra and intermolecularly associate. The theory and simulation results are found to be in excellent agreement. It is shown that the inclusion of intramolecular association can have profound effects on interfacial properties such as interfacial tension and the partition coefficient.