Is the Ewald summation still necessary? Pairwise alternatives to the accepted standard for long-range electrostatics

We investigate pairwise electrostatic interaction methods and show that there are viable computationally efficient (O(N)) alternatives to the Ewald summation for typical modern molecular simulations. These methods are extended from the damped and cutoff-neutralized Coulombic sum originally proposed by Wolf et al. [J. Chem. Phys. 110, 8255 (1999)]. One of these, the damped shifted force method, shows a remarkable ability to reproduce the energetic and dynamic characteristics exhibited by simulations employing lattice summation techniques. Comparisons were performed with this and other pairwise methods against the smooth particle-mesh Ewald summation to see how well they reproduce the energetics and dynamics of a variety of molecular simulations.     

The Langevin Hull: Constant pressure and temperature dynamics for non-periodic systems

We have developed a new isobaric-isothermal (NPT) algorithm which applies an external pressure to the facets comprising the convex hull surrounding the system. A Langevin thermostat is also applied to the facets to mimic contact with an external heat bath. This new method, the "Langevin Hull", can handle heterogeneous mixtures of materials with different compressibilities. These systems are problematic for traditional affine transform methods. The Langevin Hull does not suffer from the edge effects of boundary potential methods, and allows realistic treatment of both external pressure and thermal conductivity due to the presence of an implicit solvent. We apply this method to several different systems including bare metal nanoparticles, nanoparticles in an explicit solvent, as well as clusters of liquid water. The predicted mechanical properties of these systems are in good agreement with experimental data and previous simulation work.     

Operator algebras and a theorem of Dieudonne

LetA be aC*-algebra with second dualA″. Let (φ _n)(n=1,...) be a sequence in the dual ofA such that limφ _n(a) exists for eacha εA. In general, this does not imply that limφ _n(x) exists for eachx εA″. But if limφ _n(p) exists whenever p is the range projection of a positive self-adjoint element of the unit ball ofA, then it is shown that limφ _n(x) does exist for eachx inA″. This is a non-commutative generalisation of a celebrated theorem of Dieudonné. A new proof of Dieudonné’s theorem, for positive measures, is given here. The proof of the main result makes use of Dieudonné’s original theorem.     

Size-dependent spontaneous alloying of Au-Ag nanoparticles

We report on systematic studies of size-dependent alloy formation of silver-coated gold nanoparticles (NPs) in aqueous solution at ambient temperature using X-ray absorption fine structure spectroscopy (XAFS). Various Au-core sizes (2.5-20 nm diameter) and Ag shell thicknesses were synthesized using radiolytic wet techniques. The equilibrium structures (alloy versus core-shell) of these NPs were determined in the suspensions. We observed remarkable size dependence in the room temperature interdiffusion of the two metals. The interdiffusion is limited to the subinterface layers of the bimetallic NPs and depends on both the core size and the total particle size. For the very small particles (< or =4.6 nm initial Au-core size), the two metals are nearly randomly distributed within the particle. However, even for these small Au-core NPs, the interdiffusion occurs primarily in the vicinity of the original interface. Features from the Ag shells do remain. For the larger particles, the boundary is maintained to within one monolayer. These results cannot be explained either by enhanced self-diffusion that results from depression of the melting point with size or by surface melting of the NPs. We propose that defects, such as vacancies, at the bimetallic interface enhance the radial migration (as well as displacement around the interface) of one metal into the other. Molecular dynamics calculations correctly predict the activation energy for diffusion of the metals in the absence of vacancies and show an enormous dependence of the rate of mixing on defect levels. They also suggest that a few percent of the interfacial lattice sites need to be vacant to explain the observed mixing.     

Langevin dynamics for rigid bodies of arbitrary shape

We present an algorithm for carrying out Langevin dynamics simulations on complex rigid bodies by incorporating the hydrodynamic resistance tensors for arbitrary shapes into an advanced rotational integration scheme. The integrator gives quantitative agreement with both analytic and approximate hydrodynamic theories for a number of model rigid bodies and works well at reproducing the solute dynamical properties (diffusion constants and orientational relaxation times) obtained from explicitly solvated simulations.     

A gentler approach to RNEMD: nonisotropic velocity scaling for computing thermal conductivity and shear viscosity

We present a new method for introducing stable nonequilibrium velocity and temperature gradients in molecular dynamics simulations of heterogeneous systems. This method extends earlier reverse nonequilibrium molecular dynamics (RNEMD) methods which use momentum exchange swapping moves. The standard swapping moves can create nonthermal velocity distributions and are difficult to use for interfacial calculations. By using nonisotropic velocity scaling (NIVS) on the molecules in specific regions of a system, it is possible to impose momentum or thermal flux between regions of a simulation while conserving the linear momentum and total energy of the system. To test the method, we have computed the thermal conductivity of model liquid and solid systems as well as the interfacial thermal conductivity of a metal-water interface. We find that the NIVS-RNEMD improves the problematic velocity distributions that develop in other RNEMD methods.