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Register a new userRole of electrostatic forces in cluster formation in a dry ionomer
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This simulation study investigates the dependence of the structure of dry Nafion$^{tinytextregistered}$-like ionomers on the electrostatic interactions between the components of the molecules. In order to speed equilibration, a procedure was adopted which involved detaching the side chains from the backbone and cutting the backbone into segments, and then reassembling the macromolecule by means of a strong imposed attractive force between the cut ends of the backbone, and between the non-ionic ends of the side chains and the midpoints of the backbone segments. Parameters varied in this study include the dielectric constant, the free volume, side-chain length, and strength of head-group interactions. A series of coarse-grained mesoscale simulations shows the morphlogy to depend sensitively on the ratio of the strength of the dipole-dipole interactions between the side-chain acidic end groups to the strength of the other electrostatic components of the Hamiltonian. Examples of the two differing morphologies proposed by Gierke and by Gebel emerge from our simulations.
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Coarse-grained molecular-dynamics simulations were used to study the morphological changes induced in a Nafion$^{tiny textregistered}$-like ionomer by the imposition of a strong electric field. We observe the formation of novel structures aligned along the direction of the applied field. The polar head groups of the ionomer side chains aggregate into clusters, which then form rod-like formations which assemble into a hexatic array aligned with the direction of the field. Occasionally these lines of sulfonates and protons form a helical structure. Upon removal of the electric field, the hexatic array of rod-like structures persists, and has a lower calculated free energy than the original isotropic morphology.
We consider a model for periodic patterns of charges constrained over a cylindrical surface. In particular we focus on patterns of chiral helices, achiral rings or vertical lamellae, with the constraint of global electroneutrality. We study the dependence of the patterns size and pitch angle on the radius of the cylinder and salt concentration. We obtain a phase diagram by using numerical and analytic techniques. For pure Coulomb interactions, we find a ring phase for small radii and a chiral helical phase for large radii. At a critical salt concentration, the characteristic domain size diverges, resulting in macroscopic phase segregation of the components and restoring chiral symmetry. We discuss possible consequences and generalizations of our model.
The effect of electrostatic interactions on the stretching of DNA is investigated using a simple worm like chain model. In the limit of small force there are large conformational fluctuations which are treated using a self-consistent variational approach. For small values of the external force f, we find theoreticlly and by a simple blob picture that the extension scales as fr_D where r_D is the Debye screening length. In the limit of large force the electrostatic effects can be accounted for within the semiflexible chain model of DNA by assuming that only small excursions from rod-like conformations are possible. In this regime the extension approaches the contour length as f^{-1/2} where f is the magnitude of the external force. The theory is used to analyze experiments that have measured the extension of double-stranded DNA subject to tension at various salt concentrations. The theory reproduces nearly quantitatively the elastic response of DNA at small and large values of f and for all concentration of the monovalent counterions. The limitations of the theory are also pointed out.
Previous theoretical studies of calamitic (i.e., rod-like) ionic liquid crystals (ILCs) based on an effective one-species model led to indications of a novel smectic-A phase with a layer spacing being much larger than the length of the mesogenic (i.e., liquid-crystal forming) ions. In order to rule out the possibility that this wide smectic-A phase is merely an artifact caused by the one-species approximation, we investigate an extension which accounts explicitly for cations and anions in ILCs. Our present findings, obtained by grand canonical Monte Carlo simulations, show that the phase transitions between the isotropic and the smectic-A phases of the cation-anion system are in qualitative agreement with the effective one-species model used in the preceding studies. In particular, for ILCs with mesogenes (i.e., liquid-crystal forming species) carrying charged sites at their tips, the wide smectic-A phase forms, at low temperatures and within an intermediate density range, in between the isotropic and a hexagonal crystal phase. We find that in the ordinary smectic-A phase the spatial distribution of the counterions of the mesogens is approximately uniform, whereas in the wide smectic-A phase the small counterions accumulate in between the smectic layers. Due to this phenomenology the wide smectic-A phase could be interesting for applications which hinge on the presence of conductivity channels for mobile ions.
By means of a variational approach we study the conditions under which a polyelectrolyte in a bad solvent will undergo a transition from a rod-like structure to a ``necklace structure in which the chain collapses into a series of globules joined by stretched chain segments.
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