title: Calculation of the absolute thermodynamic properties of association of host-guest systems from the intermolecular potential of mean force.
abstract: The authors report calculations of the intermolecular potential of mean force (PMF) in the case of the host-guest interaction. The host-guest system is defined by a water soluble calixarene and a cation. With an organic cation such as the tetramethylammonium cation, the calixarene forms an insertion complex, whereas with the Lanthane cation, the supramolecular assembly is an outer-sphere complex. The authors apply a modified free energy perturbation method and the force constraint technique to establish the PMF profiles as a function of the separation distance between the host and guest. They use the PMF profile for the calculation of the absolute thermodynamic properties of association that they compare to the experimental values previously determined. They finish by giving some structural features of the insertion and outer-sphere complexes at the Gibbs free energy minimum.
authors.affiliation: Laboratoire de Thermodynamique des Solutions et des Polymères, UMR CNRS 6003, Université Blaise Pascal, 63177 Aubière Cedex, France.
authors.forename: Aziz
authors.initials: A
authors.lastname: Ghoufi
authors.forename: Patrice
authors.initials: P
authors.lastname: Malfreyt
mesh_terms: D003198:Computer Simulation; D004735:Energy Transfer; D046911:Macromolecular Substances / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D013314:Stress, Mechanical
chemical_list: D046911:Macromolecular Substances