Search results for "Boundary conditions"
showing 10 items of 97 documents
Redox potentials and acidity constants from density functional theory based molecular dynamics.
2014
CONSPECTUS: All-atom methods treat solute and solvent at the same level of electronic structure theory and statistical mechanics. All-atom computation of acidity constants (pKa) and redox potentials is still a challenge. In this Account, we review such a method combining density functional theory based molecular dynamics (DFTMD) and free energy perturbation (FEP) methods. The key computational tool is a FEP based method for reversible insertion of a proton or electron in a periodic DFTMD model system. The free energy of insertion (work function) is computed by thermodynamic integration of vertical energy gaps obtained from total energy differences. The problem of the loss of a physical refe…
Time-based Chern number in periodically driven systems in the adiabatic limit
2023
To define the topology of driven systems, recent works have proposed synthetic dimensions as a way to uncover the underlying parameter space of topological invariants. Using time as a synthetic dimension, together with a momentum dimension, gives access to a synthetic two-dimensional (2D) Chern number. It is, however, still unclear how the synthetic 2D Chern number is related to the Chern number that is defined from a parametric variable that evolves with time. Here we show that in periodically driven systems in the adiabatic limit, the synthetic 2D Chern number is a multiple of the Chern number defined from the parametric variable. The synthetic 2D Chern number can thus be engineered via h…
Non-Local Scattering Kernel and the Hydrodynamic Limit
2007
In this paper we study the interaction of a fluid with a wall in the framework of the kinetic theory. We consider the possibility that the fluid molecules can penetrate the wall to be reflected by the inner layers of the wall. This results in a scattering kernel which is a non-local generalization of the classical Maxwell scattering kernel. The proposed scattering kernel satisfies a global mass conservation law and a generalized reciprocity relation. We study the hydrodynamic limit performing a Knudsen layer analysis, and derive a new class of (weakly) nonlocal boundary conditions to be imposed to the Navier-Stokes equations.
Experimental and Theoretical Electron Density Determination for Two Norbornene Derivatives: Topological Analysis Provides Insights on Reactivity
2016
The electron density distribution of two substituted norbornene derivatives (cis-5-norbornene-endo-2,3-dicarboxylic anhydride (1) and 7-oxabicylo[2.2.1]hept-5-ene-exo-2,3-dicarboxylic anhydride (2) has been determined from low-temperature (20 K) X-ray diffraction data and from DFT calculations with periodic boundary conditions. Topological analysis of the electron density is discussed with respect to exo-selective additions, the partial retro-Diels-Alder (rDA) character of the ground state, and intermolecular interaction energies.
Unusual finite size effects in the Monte Carlo simulation of microphase formation of block copolymer melts
1995
Extensive Monte Carlo simulations are presented for the Fried-Binder model of block copolymer melts, where polymer chains are represented as self and mutually avoiding walks on a simple cubic lattice, and monomer units of different kind (A, B) repel each other if they are nearest neighbors (e AB > O). Choosing a chain length N = 20, vacancy concentration Φ v = 0,2, composition f = 3/4, and a L × L × L geometry with periodic boundary conditions and 8 ≤ L ≤ 32, finite size effects on the collective structure factor S(q) and the gyration radii are investigated. It is shown that already above the microphase separation transition, namely when the correlation length ζ(T) of concentration fluctuat…
An enhanced grain-boundary framework for computational homogenization and micro-cracking simulations of polycrystalline materials
2015
An enhanced three-dimensional (3D) framework for computational homogenization and intergranular cracking of polycrystalline materials is presented. The framework is aimed at reducing the computational cost of polycrystalline micro simulations, with an aim towards effective multiscale modelling. The scheme is based on a recently developed Voronoi cohesive-frictional grain-boundary formulation. A regularization scheme is used to avoid excessive mesh refinements often induced by the presence of small edges and surfaces in mathematically exact 3D Voronoi morphologies. For homogenization purposes, periodic boundary conditions are enforced on non-prismatic periodic micro representative volume ele…
Electronic and optical properties of carbon nanotubes under pure bending
2010
The high aspect ratio of carbon nanotubes makes them prone to bending. To know how bending affects the tubes is therefore crucial for tube identification and for electrical component design. Very few studies, however, have investigated tubes under small bending well below the buckling limit, because of technical problems due to broken translational symmetry. In this Brief Report a cost-effective and exact modeling of singe-walled nanotubes under such small bending is enabled by revised periodic boundary conditions, combined with density-functional tight-binding. The resulting, bending-induced changes in electronic and optical properties fall in clear chirality-dependent trend families. Whil…
Density-Functional Tight-Binding Simulations of Curvature-Controlled Layer Decoupling and Band-Gap Tuning in BilayerMoS2
2014
Monolayer transition-metal dichalcogenides (TMDCs) display valley-selective circular dichroism due to the presence of time-reversal symmetry and the absence of inversion symmetry, making them promising candidates for valleytronics. In contrast, in bilayer TMDCs both symmetries are present and these desirable valley-selective properties are lost. Here, by using density-functional tight-binding electronic structure simulations and revised periodic boundary conditions, we show that bending of bilayer MoS2 sheets breaks band degeneracies and localizes states on separate layers due to bending-induced strain gradients across the sheets. We propose a strategy for employing bending deformations in …
A Multiscale Approach to Polycrystalline Materials Damage and Failure
2014
A two-scale three-dimensional approach for degradation and failure in polycrystalline materials is presented. The method involves the component level and the grain scale. The damage-induced softening at the macroscale is modelled employing an initial stress boundary element approach. The microscopic degradation is explicitly modelled associating Representative Volume Elements (RVEs) to relevant points of the macro continuum and employing a cohesive-frictional 3D grain-boundary formulation to simulate intergranular degradation and failure in the Voronoi morphology. Macro-strains are downscaled as RVEs' periodic boundary conditions, while overall macro-stresses are obtained upscaling the micr…
Nonlocal Third Order Boundary Value Problems with Solutions that Change Sign
2014
We investigate the existence and the number of solutions for a third order boundary value problem with nonlocal boundary conditions in connection with the oscillatory behavior of solutions. The combination of the shooting method and scaling method is used in the proofs of our main results. Examples are included to illustrate the results.