A Monte Carlo density functional theory for the competition between inter and intramolecular association in inhomogeneous fluids

TL;DR

This paper develops a Monte Carlo density functional theory to analyze how chain length and temperature influence the competition between intra- and intermolecular association in inhomogeneous fluids, validated on a 4-mer fluid in a slit pore.

Contribution

The paper introduces a novel Monte Carlo density functional theory for associating chain molecules applicable to various chain lengths, validated against known systems.

Findings

Intramolecular association is enhanced near wall contact.

Chain length affects the balance between intra- and intermolecular bonding.

Inhomogeneity causes inversion of the chain length dependence of intermolecular bonding.

Abstract

A monte carlo density functional theory is developed for chain molecules which both intra and intermolecularly associate. The approach can be applied over a range of chain lengths. The theory is validated for the case of an associating 4-mer fluid in a planar hard slit pore. Once validated the new theory is used to study the effect of chain length and temperature on the competition between intra and intermolecular association near a hard wall. We show that this competition enhances intramolecular association near wall contact and inverts the chain length dependence of the fraction bonded intermolecularly in the inhomogeneous region.