Journal of Chemical Physics, Vol.106, No.19, 8101-8115, 1997
New Statistical-Mechanical Treatment of Systems Near Surfaces .2. Polydisperse Linear and Branched Polymers in an Athermal Solution
We apply a recently developed analytic but approximate method to study the behavior of polydisperse Linear and branched polymers in an athermal solution and near various kinds of surfaces. We consider equilibrium polydispersity controlled by a set of activities. The method allows us to account for polymer connectivity and excluded-volume effects and goes beyond the random mixing approximation. The density profiles of various kinds exhibit oscillations for bulk densities phi(mb) larger than some threshold bulk density phi(mT). The origin of these oscillations is related to the decreasing branch of the recursion function, as explained in the text. The correlation length xi’ related to these oscillations increases as phi(mb) increases. On the other hand, the correlation length xi controlling the approach of various density profiles to their respective bulk values in the range phi(mb) < phi(mT) increases as phi(mb) decreases. The free energy and the entropy are uniquely determined. Various surface properties are also easily determined. We demonstrate the existence of surface polymerization transition in the case of linear chains as surface interactions are varied, even though there is no bulk transition. The method allows us to probe the entire density range which is not possible in a Monte Carlo simulation. Our computations are ultrafast by at least three orders of magnitude compared to rival methods and easy to implement. Our results agree with Monte Carlo simulations but disagree with the mean-field predictions.