title: A Monte Carlo density functional theory for the competition between inter and intramolecular association in inhomogeneous fluids.
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.
authors.affiliation: Department of Chemical and Biomolecular Engineering, Rice University, 6100 S. Main, Houston, Texas 77005, USA.
authors.forename: Bennett D
authors.initials: BD
authors.lastname: Marshall
authors.forename: Alejandro J
authors.initials: AJ
authors.lastname: García-Cuéllar
authors.forename: Walter G
authors.initials: WG
authors.lastname: Chapman
mesh_terms: D004987:Ethers / Q000737:chemistry*; D006018:Glycols / Q000737:chemistry*; D009010:Monte Carlo Method; D011108:Polymers / Q000737:chemistry*; D011789:Quantum Theory; D013499:Surface Properties; D013696:Temperature
chemical_list: D004987:Ethers; D006018:Glycols; D011108:Polymers