We introduce a novel coarse-grained bead-spring model for flexible polymers to systematically examine the effects of an adjusted bonded potential on the formation and stability of structural macrostates in a thermal environment. The density of states obtained in advanced replica-exchange Monte Carlo simulations is analyzed by employing the recently developed generalized microcanonical inflection-point analysis method, which enables the identification of diverse structural phases and the construction of a suitably parameterized hyperphase diagram. It reveals that icosahedral phases dominate for polymers with asymmetric and narrow bond potentials, whereas polymers with symmetric and more elastic bonds tend to form amorphous structures with non-icosahedral cores. We also observe a hierarchy in the freezing transition behavior associated with the formation of the surface layer after nucleation.
In this paper, we investigate the properties of aggregation transitions in the context of generic coarse-grained homopolymer systems. By means of parallel replica-exchange Monte Carlo methods, we perform extensive simulations of systems consisting of up to 20 individual oligomer chains with five monomers each. Using the tools of the versatile microcanonical inflection-point analysis, we show that the aggregation transition is a first-order process consisting of a sequence of subtransitions between intermediate structural phases. We unravel the properties of these intermediate phases by collecting and analyzing their individual contributions towards the density of states of the system. The central theme of this systematic study revolves around translational entropy and its role in the striking phenomena of missing intermediate phases. We conclude with a brief discussion of the scaling properties of the transition temperature and the latent heat.
By means of advanced parallel replica-exchange Monte Carlo methods we examine the influence of elasticity and confinement on the structural transitions of linear systems with restricted bonded interaction. For this purpose, we adopt a model for coarse-grained flexible polymers of finite length in the dilute regime. Hyperphase diagrams are constructed using energy-dependent canonical quantities to demonstrate the effects of the changes in the range of the confined interaction on the liquid and solid structural phases. With increasing bonded interaction range we observe the disappearance of the liquid phase and the fusion of the gas-liquid (or Θ) and the liquid-solid transitions. One of the most remarkable features, the liquid-gas transition, changes from second to first order if the confined interaction range exceeds a threshold that separates polymeric from nonpolymeric systems. The notoriously difficult sampling of the entropically suppressed conformations in the region of very strong first-order transitions is improved by using multiple Gaussian modified ensembles.
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