We present a new molecularly informed statistical field theory model of inhomogeneous polarizable soft matter. The model is based on fluid elements, referred to as beads, that can carry a net monopole of charge at their center of mass and a fixed or induced dipole through a Drude-type distributed charge approach. The beads are thus polarizable and naturally manifest attractive van der Waals interactions. Beyond electrostatic interactions, beads can be given soft repulsions to sustain fluid phases at arbitrary densities. Beads of different types can be mixed or linked into polymers with arbitrary chain models and sequences of charged and uncharged beads. By such an approach, it is possible to construct models suitable for describing a vast range of soft-matter systems including electrolyte and polyelectrolyte solutions, ionic liquids, polymerized ionic liquids, polymer blends, ionomers, and block copolymers, among others. These bead models can be constructed in virtually any ensemble and converted to complex-valued statistical field theories by Hubbard-Stratonovich transforms. One of the fields entering the resulting theories is a fluctuating electrostatic potential; other fields are necessary to decouple non-electrostatic interactions. We elucidate the structure of these field theories, their consistency with macroscopic electrostatic theory in the absence and presence of external electric fields, and the way in which they embed van der Waals interactions and non-uniform dielectric properties. Their suitability as a framework for computational studies of heterogeneous soft matter systems using field-theoretic simulation techniques is discussed.

We demonstrate that small domain features (∼13 nm) can be obtained in a series of polystyrene (PS) and poly­(lactic acid) (PLA) block copolymers, PS–(PLA)2 and (PS)2–(PLA)2, that combine miktoarm molecular architectures with large interaction parameters. To supplement the experimental work, we used self-consistent field theory in tandem with the random phase approximation to explore and contrast the phase behavior of AB n and A n B n types of miktoarm block copolymers. Specifically, AB2 and A2B2 were found to be effective molecular architectures for inducing strong shifts in phase boundaries with copolymer composition and to simultaneously tune domain feature sizes. The performance of these systems is markedly different from the corresponding linear diblock copolymers and indicates the potential of macromolecular architecture control for future applications in lithography.

In self-assembly, the anisotropy of the building blocks and their formation of complex structures have been the subject of considerable recent research. Extending recent research on Janus particles and completing the study of Janus spheroids, we conduct a systematic investigation on the self-assembly of Janus prolate spheroids based on a primitive model that we proposed. Janus prolate spheroids are particles that have a prolate spheroidal body and two hemi-surfaces along the major axis coded with different chemical properties. Using Monte Carlo simulations, we investigate the effects of the aspect ratio on the self-assembly process. In contrast to the vesicle-like aggregates for Janus oblate spheroids, we obtain various ordered cluster structures for Janus prolate spheroids through self-assembly. With an increasing aspect ratio, we find a transition of cluster morphology, from vesicles to tubular micelles and micelles. In particular, a relatively small change in the aspect ratio leads to a rather significant change in morphology. We apply a cluster analysis to understand the mechanism associated with such a transition.

We present results highlighting the roles of dipolar interactions in affecting thermodynamics of diblock copolymer melts. Field theoretic methods and coarse-grained molecular dynamics (MD) simulations are used to understand the effects of dipolar interactions among copolymer segments. In particular, the effects of dipolar interactions on disorder-lamellar transition and domain spacing of the lamellar morphology are studied. It is shown that dipolar interactions stabilize the lamellar morphology over the disordered phase. Furthermore, the domain spacing for the lamellar morphology is predicted to increase with an increase in disparity between dipole moments of two kinds of monomers in the diblock or equivalently a mismatch in the dielectric constant of homopolymers forming the diblock. MD simulations reveal that additional orientational effects resulting from the anisotropic nature of the dipolar interaction potential are significant for highly polar monomers. In contrast, the field theoretic models based on orientationally averaged dipolar interaction potentials, such as those used in this work, fail to capture the effects of orientational correlations.

We present experimental and theoretical investigations of the order-disorder transition (ODT) in thin films of cylinder-forming diblock copolymers with asymmetric wetting conditions. Grazing incidence small-angle X-ray scattering (GISAXS) was implemented to determine the ODT temperatures (TODT) for poly(styrene-b-2-vinyl pyridine) (PS-P2VP) block copolymer thin films on a P2VP-preferential silicon substrate. Specifically, films consisting of multilayers of horizontally-oriented cylindrical structures (from 1- to 9-layers) were tested. We find that films with more than 2 cylindrical layers have a TODT comparable to the bulk case. However, TODT decreases as the film becomes thinner and the monolayer system has an ODT 30 °C below the bulk. Using self-consistent field theory (SCFT), we studied the ordering in corresponding thin films with asymmetric (top and bottom surface) wetting conditions. Surprisingly, SCFT is found to predict an opposite trend in TODT with film thickness than observed experimentally. Field-theoretic simulations with complex Langevin sampling were employed to resolve this discrepancy and demonstrate that thermal fluctuations in the PS-P2VP thin-film system dominate its ordering behavior in monolayer and bilayer films.

We present a molecular dynamics simulation study investigating the phase behavior of lamellae-forming diblock copolymers with a single ionic junction on the backbone. Our results show qualitative agreement with experimental findings regarding enhanced microphase separation with the introduction of an ionic junction at the conjunction point, while further revealing nonmonotonic changes in domain spacing and order–disorder transition as a function of the electrostatic interaction strength. This highlights the dominant roles of entropic and binding effects of counterions under weak and strong ionic correlations, respectively. The location of the ionic junction is found to effectively modulate the charge distribution and chain conformation in the ordered domains; its presence in the middle of a block promotes folding of the block, leading to a smaller domain size. These findings demonstrate the interplay of ionic coupling with steric hindrance and chain end effects, which enhances our understanding of the delicate control over the microphase domain features.

Using self-consistent field theory (SCFT), we explore the phase behavior of a diblock copolymer (BCP) melt in an applied electric field, with different dielectric constants assigned to each monomer type. The electric field penalizes the interfaces between species domains that are not parallel to the field. Under the present mean-field approximation, lamellar and cylindrical structures reorient to align their interfaces with the electric field, such that these mesophases will have the same electrostatic free energy contribution as the mixed (disordered) state, and their relative stability will remain unchanged. In contrast, sphere and network phases do not have an axis of dielectric uniformity; consequently, the preferred orientation and morphological response of these phases must be determined numerically. We compute the phase diagram for a BCP melt in the presence of an applied electric field by comparing the free energy of each phase at its thermodynamically preferred orientation relative to the electric field vector. We find that the stability regions of the sphere and network phases shrink with increasing field strength, in favor of the disordered, cylindrical, and lamellar phases. Moreover, the double gyroid network phase is more strongly disfavored than the orthorhombic Fddd network phase, such that the predicted region of stability for the Fddd phase is shifted to larger segregation strength (lower temperature).

We assess the roles of anisotropy and interaction range on the self-assembly of Janus colloidal particles. In particular, Monte Carlo simulation is employed to investigate the propensity for the formation of aggregates in a spheroidal model of a colloid having a relatively short-ranged interaction that is consistent with experimentally realizable systems. By monitoring the equilibrium distribution of aggregates as a function of temperature and density, we identify a "micelle" transition temperature and discuss its dependence on particle shape. We find that, unlike systems with longer ranged interactions, this system does not form micelles below a transition temperature at low density. Rather, larger clusters comprising 20-40 particles characterize the transition. We then examine the dependence of the second virial coefficient on particle shape and well width to determine how these important system parameters affect aggregation. Finally, we discuss possible strategies suggested by this work to promote self-assembly for the encapsulation of particles.