Spherical brushes within spherical cavities: a self-consistent field and Monte Carlo study.
We present an extensive numerical study on the behavior of spherical brushes confined into a spherical cavity. Self-consistent field (SCF) and off-lattice Monte Carlo (MC) techniques are used in order to determine the monomer and end-chain density profiles and the cavity pressure as a function of the brush properties. A comparison of the results obtained via SCF, MC, and the Flory theory for polymer solutions reveals SCF calculations to be a valuable alternative to MC simulations in the case of free and softly compressed brushes, while the Flory's theory accounts remarkably well for the pressure in the strongly compressed regime. In the range of high compressions, we have found the cavity pressure P to follow a scale relationship with the monomer volume fraction v, P approximately v(alpha). SCF calculations give alpha=2.15+/-0.05, whereas MC simulations lead to alpha=2.73+/-0.04. The underestimation of alpha by the SCF method is explained in terms of the inappropriate account of the monomer density correlations when a mean field approach is used.
Cerdà
Juan J
JJ
Institute for Computational Physics, Universität Stuttgart, 70569 Stuttgart, Germany. jcerda@icp.uni-stuttgart.de
Sintes
Tomás
T
Toral
Raúl
R
D008968:Molecular Conformation; D009010:Monte Carlo Method; D011108:Polymers / Q000737:chemistry; D011312:Pressure
D011108:Polymers