QM/MM simulation of liquid water with an adaptive quantum region.

The simulation of complex chemical systems often requires a multi-level description, in which a region of special interest is treated using a computationally expensive quantum mechanical (QM) model while its environment is described by a faster, simpler molecular mechanical (MM) model. Furthermore, studying dynamic effects in solvated systems or bio-molecules requires a variable definition of the two regions, so that atoms or molecules can be dynamically re-assigned between the QM and MM descriptions during the course of the simulation. Such reassignments pose a problem for traditional QM/MM schemes by exacerbating the errors that stem from switching the model at the boundary. Here we show that stable, long adaptive simulations can be carried out using density functional theory with the BLYP exchange-correlation functional for the QM model and a flexible TIP3P force field for the MM model without requiring adjustments of either. Using a primary benchmark system of pure water, we investigate the convergence of the liquid structure with the size of the QM region, and demonstrate that by using a sufficiently large QM region (with radius 6 Å) it is possible to obtain radial and angular distributions that, in the QM region, match the results of fully quantum mechanical calculations with periodic boundary conditions, and, after a smooth transition, also agree with fully MM calculations in the MM region. The key ingredient is the accurate evaluation of forces in the QM subsystem which we achieve by including an extended buffer region in the QM calculations. We also show that our buffered-force QM/MM scheme is transferable by simulating the solvated Cl(-) ion.

Self-similar breakup of near-inviscid liquids

The final stages of pinchoff and breakup of dripping droplets of near-inviscid Newtonian fluids are studied experimentally for pure water and ethanol. High-speed imaging and image analysis are used to determine the angle and the minimum neck size of the cone-shaped extrema of the ligaments attached to dripping droplets in the final microseconds before pinchoff. The angle is shown to steadily approach the value of 18.0 ±0.4, independently of the initial flow conditions or the type of breakup. The filament thins and necks following a τ2 /3 law in terms of the time remaining until pinchoff, regardless of the initial conditions. The observed behavior confirms theoretical predictions. © 2012 American Physical Society.

Self-similar breakup of near-inviscid liquids.

The final stages of pinchoff and breakup of dripping droplets of near-inviscid Newtonian fluids are studied experimentally for pure water and ethanol. High-speed imaging and image analysis are used to determine the angle and the minimum neck size of the cone-shaped extrema of the ligaments attached to dripping droplets in the final microseconds before pinchoff. The angle is shown to steadily approach the value of 18.0 ± 0.4°, independently of the initial flow conditions or the type of breakup. The filament thins and necks following a τ(2/3) law in terms of the time remaining until pinchoff, regardless of the initial conditions. The observed behavior confirms theoretical predictions.

The effect of carbon encapsulation on the magnetic properties of Ni nanoparticles produced by arc discharge in de-ionized water

Despite intensive research on optimizing the methods for depositing carbon encapsulated ferromagnetic nanoparticles, the effect of the carbon cages remains unclear. In the present work, the effect of the graphitic cages on the magnetization of the ferromagnetic core has been studied by comparing the magnetic properties of pure and carbon encapsulated Ni particles of the same size. The carbon encapsulated Ni particles were formed using an electric arc discharge in de-ionized water between a solid graphite cathode and an anode consisting of Ni and C in a mass ratio of Ni:C = 7:3. This method is shown to have potential for low cost production of carbon encapsulated Ni nanoparticle samples with narrow particle size distributions. X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM) analysis were used to study the crystallography, morphology, and size distribution of the encapsulated and pure Ni nanoparticle samples. The availability of encapsulated particles with various sizes allowed us to elucidate the role of carbon cages in size-dependent properties. Our data suggest that even though encapsulation is beneficial for protection against hostile chemical environments and for avoiding low proximity phenomena, it suppresses the saturation magnetization of the Ni cores.

Effect of water on mechanical properties of mineralized tissue composites

In the current study, the effects of polar solvents on tissue volume and mechanical properties are considered. Area shrinkage measurements are conducted for mineralized bone tissue samples soaked in polar solvents. Area shrinkage is used to calculate approximate linear and volume shrinkage. Results are compared with viscoelastic mechanical parameters for bone in the same solvents (as measured previously) and with both shrinkage measurements and mechanical data for nonmineralized tissues, as taken from the existing literature. As expected, the shrinkage of mineralized tissues is minimal when compared with shrinkage of nonmineralized tissues immersed in the same polar solvents. The mechanical changes in bone are also substantially less than in nonmineralized tissues. The largest stiffness values are found in shrunken bone samples (immersed in acetone and ethanol). The mineral phase in bone thus resists tissue shrinkage that would otherwise occur in the pure soft tissue phase. © 2007 Materials Research Society.

The dominant role of the solvent-water interface in water droplet templating of polymers

We investigate the formation of microstructured polymer networks known as Breath Figure templated structures created by the presence of water vapour over evaporating polymer solutions. We use a highly controlled experimental approach to examine this dynamic and non-equilibrium process to uniquely compare pure solvent systems with polymer solutions and demonstrate using a combination of optical microscopy, focused ion-beam milling and SEM analysis that the porous polymer microstructure is completely controlled by the interfacial forces that exist between the water droplet and the solvent until a final drying dilation of the imprints. Water droplet contact angles are the same in the presence or absence of polymer and are independent of size for droplets above 5 μm. The polymer acts a spectator that serves to trap water droplets present at the air interface, and to transfer their shape into the polymer film. For the smallest pores, however, there are unexpected variations in the contact angle with pore size that are consistent with a possible contribution from line tension at these smaller dimensions. © The Royal Society of Chemistry.