Emergent Properties from Three-Dimensional Assemblies of (Nano)particles in Confined Spaces.

The assembly of (nano)particles into compact hierarchical structures yields emergent properties not found in the individual constituents. The formation of these structures relies on a profound knowledge of the nanoscale interactions between (nano)particles, which are often designed by researchers aided by computational studies. These interactions have an effect when the (nano)particles are brought into close proximity, yet relying only on diffusion to reach these closer distances may be inefficient.

Simple and Accurate One-Body Energy and Dipole Moment Surfaces for Water and Beyond.

Water is often the testing ground for new, advanced force fields. While advanced functional forms for intermolecular interactions have been integral to the development of accurate water models, less attention has been paid to a transferable model for intramolecular valence terms. In this work, we present a one-body energy and dipole moment surface model, named 1B-UCB, that is simple yet accurate and can be feasibly adapted for both standard and advanced potentials.

The role of charge in microdroplet redox chemistry.

In charged water microdroplets, which occur in nature or in the lab upon ultrasonication or in electrospray processes, the thermodynamics for reactive chemistry can be dramatically altered relative to the bulk phase. Here, we provide a theoretical basis for the observation of accelerated chemistry by simulating water droplets of increasing charge imbalance to create redox agents such as hydroxyl and hydrogen radicals and solvated electrons. We compute the hydration enthalpy of OH and H that controls the electron transfer process, and the corresponding changes in vertical ionization energy and vertical electron affinity of the ions, to create OH and H reactive species.

Predicting the Raman Spectra of Liquid Water with a Monomer-Field Model.

The Raman spectrum of liquid water is quite complex, reflecting its strong sensitivity to the local environment of the individual waters. The OH-stretch region of the spectrum, which captures the influence of hydrogen bonding, has only just begun to be unraveled. Here we develop a model for predicting the Raman spectra of the OH-stretch region by considering how local electric fields distort the energy surface of each water monomer.

M-Chem: a Modular Software Package for Molecular Simulation that Spans Scientific Domains.

We present a new software package called M-Chem that is designed from scratch in C++ and parallelized on shared-memory multi-core architectures to facilitate efficient molecular simulations. Currently, M-Chem is a fast molecular dynamics (MD) engine that supports the evaluation of energies and forces from two-body to many-body all-atom potentials, reactive force fields, coarse-grained models, combined quantum mechanics molecular mechanics (QM/MM) models, and external force drivers from machine learning, augmented by algorithms that are focused on gains in computational simulation times. M-Chem also includes a range of standard simulation capabilities including thermostats, barostats, multi-timestepping, and periodic cells, as well as newer methods such as fast extended Lagrangians and high quality electrostatic potential generation.

Self-Assembly of Atomically Aligned Nanoparticle Superlattices from Pt-FeO Heterodimer Nanoparticles.

Multicomponent nanoparticle superlattices (SLs) promise the integration of nanoparticles (NPs) with remarkable electronic, magnetic, and optical properties into a single structure. Here, we demonstrate that heterodimers consisting of two conjoined NPs can self-assemble into novel multicomponent SLs with a high degree of alignment between the atomic lattices of individual NPs, which has been theorized to lead to a wide variety of remarkable properties. Specifically, by using simulations and experiments, we show that heterodimers composed of larger FeO domains decorated with a Pt domain at one vertex can self-assemble into an SL with long-range atomic alignment between the FeO domains of different NPs across the SL.

Spontaneous Formation of Hydrogen Peroxide in Water Microdroplets.

There is accumulating evidence that many chemical reactions are accelerated by several orders of magnitude in micrometer-sized aqueous or organic liquid droplets compared to their corresponding bulk liquid phase. However, the molecular origin of the enhanced rates remains unclear as in the case of spontaneous appearance of 1 μM hydrogen peroxide in water microdroplets. In this Letter, we consider the range of ionization energies and whether interfacial electric fields of a microdroplet can feasibly overcome the high energy step from hydroxide ions (OH) to hydroxyl radicals (OH) in a primary HO mechanism.

Tuning Stoichiometry to Promote Formation of Binary Colloidal Superlattices.

The self-assembly of binary nanoparticle superlattices from colloidal mixtures is a promising method for the fabrication of complex colloidal cocrystal structures. However, binary mixtures often form amorphous or metastable phases instead of the thermodynamically stable phase. Here we show that in binary mixtures of differently sized spherical particles, an excess of the smaller component can promote-and, in some cases, may be necessary for-the self-assembly of a binary cocrystal.

Influence of Softness on the Stability of Binary Colloidal Crystals.

Mixtures of two types of nanoparticles can self-assemble into a wide variety of binary colloidal crystals (also called binary nanoparticle superlattices), which are interesting for their structural diversity and potential applications. Although so-called packing models-which usually treat the particles as "hard" with only excluded volume interactions-seem to explain many reported dense crystalline phases, these models often fail to predict the right structure. Here, we examine the role of soft repulsive interparticle interactions on binary colloidal crystals comprising two sizes of spherical particles; such "softness" can arise due to ligand shells or screened electrostatics.