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

Ligand-stabilized copper selenide (Cu2-xSe) nanocrystals, approximately 16 nm in diameter, were synthesized by a colloidal hot injection method and coated with amphiphilic polymer. The nanocrystals readily disperse in water and exhibit strong near-infrared (NIR) optical absorption with a high molar extinction coefficient of 7.7 × 107 cm–1 M–1 at 980 nm. When excited with 800 nm light, the Cu2-xSe nanocrystals produce significant photothermal heating with a photothermal transduction efficiency of 22%, comparable to nanorods and nanoshells of gold (Au). In vitro photothermal heating of Cu2-xSe nanocrystals in the presence of human colorectal cancer cell (HCT-116) led to cell destruction after 5 min of laser irradiation at 33 W/cm2, demonstrating the viabilitiy of Cu2-xSe nanocrystals for photothermal therapy applications.

Copper selenide nanocrystals for photothermal therapy.

Solar illumination of broadly absorbing metal or carbon nanoparticles dispersed in a liquid produces vapor without the requirement of heating the fluid volume. When particles are dispersed in water at ambient temperature, energy is directed primarily to vaporization of water into steam, with a much smaller fraction resulting in heating of the fluid. Sunlight-illuminated particles can also drive H2O–ethanol distillation, yielding fractions significantly richer in ethanol content than simple thermal distillation. These phenomena can also enable important compact solar applications such as sterilization of waste and surgical instruments in resource-poor locations.

Solar Vapor Generation Enabled by Nanoparticles

Photothermal ablation (PTA) therapy has a great potential to revolutionize conventional therapeutic approaches for cancers, but it has been limited by difficulties in obtaining biocompatible photothermal agents that have low cost, small size (<100 nm), and high photothermal conversion efficiency. Herein, we have developed hydrophilic plate-like Cu(9)S(5) nanocrystals (NCs, a mean size of ∼70 nm × 13 nm) as a new photothermal agent, which are synthesized by combining a thermal decomposition and ligand exchange route. The aqueous dispersion of as-synthesized Cu(9)S(5) NCs exhibits an enhanced absorption (e.g., ∼1.2 × 10(9) M(-1) cm(-1) at 980 nm) with the increase of wavelength in near-infrared (NIR) region, which should be attributed to localized surface plasmon resonances (SPR) arising from p-type carriers. The exposure of the aqueous dispersion of Cu(9)S(5) NCs (40 ppm) to 980 nm laser with a power density of 0.51 W/cm(2) can elevate its temperature by 15.1 °C in 7 min; a 980 nm laser heat conversion efficiency reaches as high as 25.7%, which is higher than that of the as-synthesized Au nanorods (23.7% from 980 nm laser) and the recently reported Cu(2-x)Se NCs (22% from 808 nm laser). Importantly, under the irradiation of 980 nm laser with the conservative and safe power density over a short period (∼10 min), cancer cells in vivo can be efficiently killed by the photothermal effects of the Cu(9)S(5) NCs. The present finding demonstrates the promising application of the Cu(9)S(5) NCs as an ideal photothermal agent in the PTA of in vivo tumor tissues.

Hydrophilic Cu9S5 Nanocrystals: A Photothermal Agent with a 25.7% Heat Conversion Efficiency for Photothermal Ablation of Cancer Cells in Vivo

Photothermal materials with broad solar absorption and high conversion efficiency have recently attracted significant interest. They are becoming a fast-growing research focus in the area of solar-driven vaporization for clean water production. The parallel development of thermal management strategies through both material and system designs has further improved the overall efficiency of solar vaporization. Collectively, this green solar-driven water vaporization technology has regained attention as a sustainable solution for water scarcity. In this review, we will report the recent progress in solar absorber material design based on various photothermal conversion mechanisms, evaluate the prerequisites in terms of optical, thermal and wetting properties for efficient solar-driven water vaporization, classify the systems based on different photothermal evaporation configurations and discuss other correlated applications in the areas of desalination, water purification and energy generation. This article aims to provide a comprehensive review on the current development in efficient photothermal evaporation, and suggest directions to further enhance its overall efficiency through the judicious choice of materials and system designs, while synchronously capitalizing waste energy to realize concurrent clean water and energy production.

Solar absorber material and system designs for photothermal water vaporization towards clean water and energy production

Visible radiation at resonant frequencies is transduced to thermal energy by surface plasmons on gold nanoparticles. Temperature in ≤10-microliter aqueous suspensions of 20-nanometer gold particles irradiated by a continuous wave Ar+ ion laser at 514 nm increased to a maximum equilibrium value. This value increased in proportion to incident laser power and in proportion to nanoparticle content at low concentration. Heat input to the system by nanoparticle transduction of resonant irradiation equaled heat flux outward by conduction and radiation at thermal equilibrium. The efficiency of transducing incident resonant light to heat by microvolume suspensions of gold nanoparticles was determined by applying an energy balance to obtain a microscale heat-transfer time constant from the transient temperature profile. Measured values of transduction efficiency were increased from 3.4% to 9.9% by modulating the incident continuous wave irradiation.

Microscale Heat Transfer Transduced by Surface Plasmon Resonant Gold Nanoparticles.

Asphaltenes are a solubility class of petroleum crude oil that can destabilize and deposit in both upstream and downstream processes. In this study, asphaltene deposits were generated in metal capillaries by heptane addition to crude oils, and it was found that deposition is caused by submicrometer asphaltene aggregates. Deposits were generated at heptane concentrations above and significantly below the instantaneous onset point. Analysis of the results reveals that the governing factor controlling the magnitude of asphaltene deposition is the concentration of insoluble asphaltenes present in a crude oil-precipitant mixture and the instantaneous onset point is irrelevant to the deposition process. Electron microscopy images of the deposits represent the first images and confirmation of arterial growth in laboratory generated asphaltene deposits. The axial deposit profile was found to be highly nonuniform. In addition, deposits formed shortly after when oil and heptane mix, revealing that the destabilizati...

A Fundamental Study of Asphaltene Deposition

This paper discusses time-resolved small-angle neutron scattering results that were used to investigate asphaltene structure and stability with and without a precipitant added in both crude oil and model oil. A novel approach was used to isolate the scattering from asphaltenes that are insoluble and in the process of aggregating from those that are soluble. It was found that both soluble and insoluble asphaltenes form fractal clusters in crude oil and the fractal dimension of the insoluble asphaltene clusters is higher than that of the soluble clusters. Adding heptane also increases the size of soluble asphaltene clusters without modifying the fractal dimension. Understanding the process of insoluble asphaltenes forming fractals with higher fractal dimensions will potentially reveal the microscopic asphaltene destabilization mechanism (i.e., how a precipitant modifies asphaltene-asphaltene interactions). It was concluded that because of the polydisperse nature of asphaltenes, no well-defined asphaltene ph...

The Fractal Aggregation of Asphaltenes

This study discusses the development of a generalized geometric population balance model for simulating the growth of asphaltene aggregates from the nanometer scale to micrometer-sized particles. The Smoluchowski kernel has been incorporated to describe the aggregation of asphaltene nanoaggregates, which is induced by the addition of a precipitant, e.g., heptane. Rather than using the discretization of particle sizes based on the particle volumes, a discretization scheme based on the number of asphaltene molecules is incorporated, which ensures that the mass is conserved in this model. The model is in good agreement with the experimental data for the evolution of asphaltene aggregates at different times collected by centrifugation. The particle size distribution (PSD) of the asphaltene aggregates as a function of time is also determined. It was observed that the shift of the PSD to larger diameters is faster in the case of higher heptane concentrations because of the greater mass of asphaltenes precipitat...

Modeling the Aggregation of Asphaltene Nanoaggregates in Crude Oil−Precipitant Systems

Small-angle X-ray and neutron scattering (SAXS/SANS) by asphaltenes in various solvents (toluene, tetrahydrofuran, and 1-methylnaphthalene) at dilute concentrations of asphaltenes are presented and discussed. As asphaltenes are diluted, it was found that the cluster size decreases and follows a fractal scaling law. This observation reveals that asphaltene clusters persist to dilute concentrations and maintain fractal characteristics, regardless of concentration. For the first time, the fraction of asphaltenes that exist in nanoaggregates compared to those molecularly dispersed was estimated from the scattering intensity. Significant dissociation was detected at concentrations similar to the previously reported critical nanoaggregate concentration (CNAC); however, the dissociation was observed to occur gradually as the asphaltene concentration was lowered. Complete dissociation was not detected, and aggregates persisted down to asphaltene concentrations as low as 15 mg/L (0.00125 vol. %). A simplified ther...

Michael P. Hoepfner

Papers

Microscale Heat Transfer Transduced by Surface Plasmon Resonant Gold Nanoparticles.

A Fundamental Study of Asphaltene Deposition

The Fractal Aggregation of Asphaltenes

Modeling the Aggregation of Asphaltene Nanoaggregates in Crude Oil−Precipitant Systems

Multiscale scattering investigations of asphaltene cluster breakup, nanoaggregate dissociation, and molecular ordering.