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

J Chem Phys. 2013 May 28;138(20):204908. doi: 10.1063/1.4807587.

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Ethers / chemistry*
  • Glycols / chemistry*
  • Monte Carlo Method
  • Polymers / chemistry*
  • Quantum Theory*
  • Surface Properties
  • Temperature

Substances

  • Ethers
  • Glycols
  • Polymers