Three parallel algorithms for classical molecular dynamics are presented. The first assigns each processor a fixed subset of atoms; the second assigns each a fixed subset of inter-atomic forces to compute; the third assigns each a fixed spatial region. The algorithms are suitable for molecular dynamics models which can be difficult to parallelize efficiently—those with short-range forces where the neighbors of each atom change rapidly. They can be implemented on any distributed-memory parallel machine which allows for message-passing of data between independently executing processors. The algorithms are tested on a standard Lennard-Jones benchmark problem for system sizes ranging from 500 to 100,000,000 atoms on several parallel supercomputers--the nCUBE 2, Intel iPSC/860 and Paragon, and Cray T3D. Comparing the results to the fastest reported vectorized Cray Y-MP and C90 algorithm shows that the current generation of parallel machines is competitive with conventional vector supercomputers even for small problems. For large problems, the spatial algorithm achieves parallel efficiencies of 90% and a 1840-node Intel Paragon performs up to 165 faster than a single Cray C9O processor. Trade-offs between the three algorithms and guidelines for adapting them to more complex molecular dynamics simulations are also discussed.

Fast parallel algorithms for short-range molecular dynamics

We review direct force measurements on a broad class of hydrophobic and hydrophilic surfaces. These measurements have enabled the development of a general interaction potential per unit area, W(D) = -2γ(i)Hy exp(-D/D(H)) in terms of a nondimensional Hydra parameter, Hy, that applies to both hydrophobic and hydrophilic interactions between extended surfaces. This potential allows one to quantitatively account for additional attractions and repulsions not included in the well-known combination of electrostatic double layer and van der Waals theories, the so-called Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The interaction energy is exponentially decaying with decay length D(H) ≈ 0.3-2 nm for both hydrophobic and hydrophilic interactions, with the exact value of D(H) depending on the precise system and conditions. The pre-exponential factor depends on the interfacial tension, γ(i), of the interacting surfaces and Hy. For Hy > 0, the interaction potential describes interactions between partially hydrophobic surfaces, with the maximum hydrophobic interaction (i.e., two fully hydrophobic surfaces) corresponding to Hy = 1. Hydrophobic interactions between hydrophobic monolayer surfaces measured with the surface forces apparatus (SFA) are shown to be well described by the proposed interaction potential. The potential becomes repulsive for Hy < 0, corresponding to partially hydrophilic (hydrated) interfaces. Hydrated surfaces such as mica, silica, and lipid bilayers are discussed and reviewed in the context of the values of Hy appropriate for each system.

Developing a General Interaction Potential for Hydrophobic and Hydrophilic Interactions in Self-Assembled Systems

Safe and clean water is of pivotal importance to all living species and the ecosystem on earth. However, the accelerating economy and industrialization of mankind generate water pollutants with much larger quantity and higher complexity than ever before, challenging the efficacy of traditional water treatment technologies. The flourishing researches on nanomaterials and nanotechnologies in the past decade have generated new understandings on many fundamental processes and brought revolutionary upgrades to various traditional technologies in almost all areas, including water treatment. An indispensable step toward the real application of nanomaterials in water treatment is to confine them in large processable substrate to address various inherent issues, such as spontaneous aggregation, difficult operation and potential environmental risks. Strikingly, when the size of the spatial restriction provided by the substrate is on the order of only one or several nanometers, referred to as nanoconfinement, the phase behavior of matter and the energy diagram of a chemical reaction could be utterly changed. Nevertheless, the relationship between such changes under nanoconfinement and their implications for water treatment is rarely elucidated systematically. In this Critical Review, we will briefly summarize the current state-of-the-art of the nanomaterials, as well as the nanoconfined analogues (i.e., nanocomposites) developed for water treatment. Afterward, we will put emphasis on the effects of nanoconfinement from three aspects, that is, on the structure and behavior of water molecules, on the formation (e.g., crystallization) of confined nanomaterials, and on the nanoenabled chemical reactions. For each aspect, we will build the correlation between the nanoconfinement effects and the current studies for water treatment. More importantly, we will make proposals for future studies based on the missing links between some of the nanoconfinement effects and the water treatment technologies. Through this Critical Review, we aim to raise the research attention on using nanoconfinement as a fundamental guide or even tool to advance water treatment technologies.

Nanoconfinement-Mediated Water Treatment: From Fundamental to Application.

The production of molecular hydrogen by catalyzing water splitting is central to achieving the decarbonization of sustainable fuels and chemical transformations. In this work, a series of structure-making/breaking cations in the electrolyte were investigated as spectator cations in hydrogen evolution and oxidation reactions (HER/HOR) in the pH range of 1 to 14, whose kinetics was found to be altered by up to 2 orders of magnitude by these cations. The exchange current density of HER/HOR was shown to increase with greater structure-making tendency of cations in the order of Cs+ < Rb+ < K+ < Na+ < Li+, which was accompanied by decreasing reorganization energy from the Marcus-Hush-Chidsey formalism and increasing reaction entropy. Invoking the Born model of reorganization energy and reaction entropy, the static dielectric constant of the electrolyte at the electrified interface was found to be significantly lower than that of bulk, decreasing with the structure-making tendency of cations at the negatively charged Pt surface. The physical origin of cation-dependent HER/HOR kinetics can be rationalized by an increase in concentration of cations on the negatively charged Pt surface, altering the interfacial water structure and the H-bonding network, which is supported by classical molecular dynamics simulation and surface-enhanced infrared absorption spectroscopy. This work highlights immense opportunities to control the reaction rates by tuning interfacial structures of cation and solvents.

Cation- and pH-Dependent Hydrogen Evolution and Oxidation Reaction Kinetics.

In this Focus Review, we put the spotlight on very recent insights into the fascinating world of wet chemistry in the realm offered by nanoconfinement of water in mechanically rather rigid and chemically inert planar slit pores wherein only monolayer and bilayer water lamellae can be hosted. We review the effect of confinement on different aspects such as hydrogen bonding, ion diffusion, and charge defect migration of H+(aq) and OH-(aq) in nanoconfined water depending on slit pore width. A particular focus is put on the strongly modulated local dielectric properties as quantified in terms of anisotropic polarization fluctuations across such extremely confined water films and their putative effects on chemical reactions therein. The stunning findings disclosed only recently extend wet chemistry in particular and solvation science in general toward extreme molecular confinement conditions.

Confinement-Controlled Aqueous Chemistry within Nanometric Slit Pores.

The dielectric constant for water is reduced under confinement. Although this phenomenon is well known, the underlying physical mechanism for the reduction is still in debate. In this work, we investigate the effect of the orientation of hydrogen bonds on the dielectric properties of confined water using molecular dynamics simulations. We find a reduced rotational diffusion coefficient for water molecules close to the solid surface. The reduced rotational diffusion arises due to the hindered rotation away from the plane parallel to the channel walls. The suppressed rotation in turn affects the orientational polarization of water, leading to a low value for the dielectric constant at the interface. We attribute the constrained out-of-plane rotation to originate from a higher density of planar hydrogen bonds formed by the interfacial water molecules.

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Sleeba Varghese

Papers

Effect of Hydrogen Bonds on the Dielectric Properties of Interfacial Water.