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

摘要

A Monte Carlo density functional theory is developed for chain molecules which both intra andintermolecularly associate. The approach can be applied over a range of chain lengths. The theoryis 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 competitionbetween intra and intermolecular association near a hard wall. We show that this competitionenhances intramolecular association near wall contact and inverts the chain length dependence ofthe fraction bonded intermolecularly in the inhomogeneous region.