Search

Molecular dynamics studies of two generalized forms of the rough sphere model are reported. The generalization permits us to vary the coupling between rotational and translational motion through a stick parameter λ. The autocorrelation functions show deviations from the Enskog theory for all values of λ studied—indicating that collective effects are involved. It appears that the angular velocity correlation function is the sum of two exponentials. A simulation of a mixture of disparate sized rough spheres was also performed. It is found that the rotational motion of the small particle is not significantly altered upon introduction of the large particles, but the linear velocity correlation function of the small particle differes considerably from that of the neat fluid (in the time regime from 5–15 mean collision time units).

The hydrophobic interaction between two apolar (Lennard–Jones) spheres dissolved in a model of liquid water (ST 2 water) is simulated using the force‐bias Monte Carlo technique recently devised by the authors. Importance sampling techniques are devised and used to give a relatively accurate determination of the potential of mean force of the two apolar spheres as a function of their separation. This determination shows that there are two relatively stable configurations for the spheres. In one configuration each member of the pair sits in its own water cage with one water molecule fitting between them. There is a free energy barrier separating this from the other stable configuration which is such that no water molecule sits between the spheres. This conclusion is shown to be quantitatively consistent with the recent semiempirical theory of Pratt and Chandler and is in disagreement with some previous Monte Carlo studies.

The structure of ST2 water around a pair of spherical nonpolar (Lennard‐Jones) particles, A1–A2, is studied as a function of pair separation, r, using a force‐bias Monte Carlo technique with importance sampling. The change in the water structure (or equivalently the hydrophobic hydration) is correlated with the potential of mean force, WAA (r), determined in a previous study. It is found that the second minimum in WAA (r) corresponds to a water molecule lying between the two apolar particles. The water always maintains a ’’linear hydrogen bond’’ network and is more ordered in the neighborhood of the two spheres except possibly when they are separated by a distance corresponding to the position of the free energy barrier, that is the maximum in WAA (r).