Abstrakt
The target of this work is to study conformational properties of starlike polyelectrolytes with pH-sensitive (annealed) dissociation in salt-free solutions. We confront hybrid Monte Carlo (HMC) simulations with computationally less expensive approximate numerical self-consistentfield (SCF) calculations and with analytical theories.
We demonstrate when the meanfi-eld results are reliable and their advantage over MC in terms of efficiency can be exploited and when not. In the interior of the star, where inter-arm interactions dominate over intra-arm ones, the mean-field approximation works well and SCF agrees with the MC results.
Intra-arm interactions dominate at star periphery, and their role is underestimated by the mean field. Here, conformations and dissociation resemble those of linear polyelectrolytes.
Consequently,the dissociation profile along the chain contour is qualitatively different between MC and SCF. Comparison of the two methodsand a distinction between intra-arm and inter-arm contributions to interactions enables us to understand the transition in behavior from linear to starlike chain topology.