Consistent coarse-graining strategy for polymer solutions in the thermal crossover from Good to Theta solvent

Abstract

We extend our previously developed coarse-graining strategy for linear polymers with a tunable number n of effective atoms (blobs) per chain [D'Adamo et al., J. Chem. Phys. 137, 4901 (2012)] to polymer systems in thermal crossover between the good-solvent and the Theta regimes. We consider the thermal crossover in the region in which tricritical effects can be neglected, i.e. not too close to the Theta point, for a wide range of chain volume fractions Phi=c/c* (c* is the overlap concentration), up to Phi=30. Scaling crossover functions for global properties of the solution are obtained by Monte-Carlo simulations of the Domb-Joyce model. They provide the input data to develop a minimal coarse-grained model with four blobs per chain. As in the good-solvent case, the coarse-grained model potentials are derived at zero density, thus avoiding the inconsistencies related to the use of state-dependent potentials. We find that the coarse-grained model reproduces the properties of the underlying system up to some reduced density which increases when lowering the temperature towards the Theta state. Close to the lower-temperature crossover boundary, the tetramer model is accurate at least up to Phi<10, while near the good-solvent regime reasonably accurate results are obtained up to Phi<2. The density region in which the coarse-grained model is predictive can be enlarged by developing coarse-grained models with more blobs per chain. We extend the strategy used in the good-solvent case to the crossover regime. This requires a proper treatment of the length rescalings as before, but also a proper temperature redefinition as the number of blobs is increased. The case n=10 is investigated. Comparison with full-monomer results shows that the density region in which accurate predictions can be obtained is significantly wider than that corresponding to the n=4 case.

21 pages, 14 figures

References in corpus (12)

• Beware of density dependent pair potentials
• Accurate estimate of the critical exponent $\nu$ for self-avoiding walks via a fast implementation of the pivot algorithm
• Efficient implementation of the pivot algorithm for self-avoiding walks
• Influence of solvent quality on effective pair potentials between polymers in solution
• A multi-blob representation of semi-dilute polymer solutions
• Thermodynamic consistency in variable-level coarse-graining of polymeric liquids
• Virial coefficients and osmotic pressure in polymer solutions in good-solvent conditions
• Coarse-graining strategies in polymer solutions
• Predicting the thermodynamics by using state-dependent interactions
• Polymers as compressible soft spheres
• Influence of solvent quality on polymer solutions: a Monte Carlo study of bulk and interfacial properties
• Two-parameter model predictions and theta-point crossover for linear-polymer solutions

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