We have performed extensive classical molecular dynamics simulations to examine the molecular transport mechanisms of I-, Br-, Cl-, and Na+ ions across the liquid/vapor interface of water. The potentials of mean force were calculated using the constrained mean force approach and polarizable potential models were used to describe the interactions among the species. The simulated potentials of mean force were found to be different,. depending on the type of anion. The larger I-and Br- anions bind more strongly to the liquid/ vapor interface of water than that of the smaller Cl- ion. It is important to note that most of the gas phase and solution phase properties of the Br- anion are quite similar to that of the Cl- ion. At the interface, however, the interactions of the Br-and Cl- anions with the water interface appeared to be significantly different. We found that the anions approach the interface more closely than cations. We have also studied the transport mechanism of an I- across the water/dichloromethane interface. The computed potential of mean force showed no Well-defined minimum as in the liquid/vapor case, but a stabilization free energy of about -1 kcal/mol near the interface with respect to the bulk liquid was observed. The I-anion carried a water molecule with it as it crossed the interface. This result is in agreement with a recent experimental study on a similar system. Our work differs from earlier contributions in that our potential models have taken many-body effects into account, and in some cases, these effects cannot be neglected.