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

作者：Marshall Bennett D; Garcia Cuellar Alejandro J; Chapman Walter G^*

来源：Journal of Chemical Physics, 2013, 138(20): 204908.

DOI：10.1063/1.4807587

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.

• 出版日期2013-5-28