Water in an External Electric Field: Comparing Charge Distribution Methods Using ReaxFF Simulations.

The growing interest in the effects of external electric fields on reactive processes requires predictive methods that can reach longer length and time scales than quantum mechanical simulations. Recently, many studies have included electric fields in ReaxFF, a widely used reactive molecular dynamics method. In the case of modeling an external electric field, the charge distribution method used in ReaxFF is critical.

Recent Advances for Improving the Accuracy, Transferability, and Efficiency of Reactive Force Fields.

Reactive force fields provide an affordable model for simulating chemical reactions at a fraction of the cost of quantum mechanical approaches. However, classically accounting for chemical reactivity often comes at the expense of accuracy and transferability, while computational cost is still large relative to nonreactive force fields. In this Perspective, we summarize recent efforts for improving the performance of reactive force fields in these three areas with a focus on the ReaxFF theoretical model.

Effect of an external field on capillary waves in a dipolar fluid.

The role of an external field on capillary waves at the liquid-vapor interface of a dipolar fluid is investigated using molecular dynamics simulations. For fields parallel to the interface, the interfacial width squared increases linearly with respect to the logarithm of the size of the interface across all field strengths tested. The value of the slope decreases with increasing field strength, indicating that the field dampens the capillary waves.

Fluctuation Effects on the Brush Structure of Mixed Brush Nanoparticles in Solution.

A potentially attractive way to control nanoparticle assembly is to graft one or more polymers on the nanoparticle, to control the nanoparticle-nanoparticle interactions. When two immiscible polymers are grafted on the nanoparticle, they can microphase separate to form domains at the nanoparticle surface. Here, we computationally investigate the phase behavior of such binary mixed brush nanoparticles in solution, across a large and experimentally relevant parameter space.

Field-theoretic simulations of block copolymer nanocomposites in a constant interfacial tension ensemble.

Block copolymers, due to their ability to self-assemble into periodic structures with long range order, are appealing candidates to control the ordering of functionalized nanoparticles where it is well-accepted that the spatial distribution of nanoparticles in a polymer matrix dictates the resulting material properties. The large parameter space associated with block copolymer nanocomposites makes theory and simulation tools appealing to guide experiments and effectively isolate parameters of interest. We demonstrate a method for performing field-theoretic simulations in a constant volume-constant interfacial tension ensemble (nVγT) that enables the determination of the equilibrium properties of block copolymer nanocomposites, including when the composites are placed under tensile or compressive loads.

Solvent vapor annealing in block copolymer nanocomposite films: a dynamic mean field approach.

Polymer nanocomposites are an important class of materials due to the nanoparticles' ability to impart functionality not commonly found in a polymer matrix, such as electrical conductivity or tunable optical properties. While the equilibrium properties of polymer nanocomposites can be treated using numerous theoretical and simulation approaches, in experiments the effects of processing and kinetic traps are significant and thus critical for understanding the structure and the functionality of polymer nanocomposites. However, simulation methods that can efficiently predict kinetically trapped and metastable structures of polymer nanocomposites are currently not common.

Predicting the structure and interfacial activity of diblock brush, mixed brush, and Janus-grafted nanoparticles.

A modeling framework is developed to describe the structure and properties of fluid interfaces stabilized with grafted nanoparticles. The framework is demonstrated on nanoparticles functionalized with polymers of various grafting architectures; we find that the conformation of the grafted chains plays an important role in the interfacial tension.

Field theoretic simulations of polymer nanocomposites.

Polymer field theory has emerged as a powerful tool for describing the equilibrium phase behavior of complex polymer formulations, particularly when one is interested in the thermodynamics of dense polymer melts and solutions where the polymer chains can be accurately described using Gaussian models. However, there are many systems of interest where polymer field theory cannot be applied in such a straightforward manner, such as polymer nanocomposites. Current approaches for incorporating nanoparticles have been restricted to the mean-field level and often require approximations where it is unclear how to improve their accuracy.

Size-controlled self-assembly of superparamagnetic polymersomes.

We report the size-controlled self-assembly of polymersomes through the cooperative self-assembly of nanoparticles and amphiphilic polymers. Polymersomes densely packed with magnetic nanoparticles in the polymersome membrane (magneto-polymersome) were fabricated with a series of different sized iron oxide nanoparticles. The distribution of nanoparticles in a polymersome membrane was size-dependent; while small nanoparticles were dispersed in a polymer bilayer, large particles formed a well-ordered superstructure at the interface between the inner and outer layer of a bilayer membrane.