We formulate a theory of non-equilibrium statistical thermodynamics for ensembles of atoms or molecules. The theory is an application of Jayne's maximum entropy principle, which allows the statistical treatment of systems away from equilibrium. In particular, neither temperature nor atomic fractions are required to be uniform but instead are allowed to take different values from particle to particle. In addition, following the Coleman-Noll method of continuum thermodynamics we derive a dissipation inequality expressed in terms of discrete thermodynamic fluxes and forces. This discrete dissipation inequality effectively sets the structure for discrete kinetic potentials that couple the microscopic field rates to the corresponding driving forces, thus resulting in a closed set of equations governing the evolution of the system. We complement the general theory with a variational meanfield theory that provides a basis for the formulation of computationally tractable approximations. We present several validation cases, concerned with equilibrium properties of alloys, heat conduction in silicon nanowires and hydrogen desorption from palladium thin films, that demonstrate the range and scope of the method and assess its fidelity and predictiveness. These validation cases are characterized by the need or desirability to account for atomiclevel properties while simultaneously entailing time scales much longer than * Corresponding author E-mail address: ortiz@caltech.edu (M. Ortiz). September 27, 2014 those accessible to direct molecular dynamics. The ability of simple meanfield models and discrete kinetic laws to reproduce equilibrium properties and long-term behavior of complex systems is remarkable. Preprint submitted to Journal of the Mechanics and Physics of Solids

a b s t r a c tThe quasicontinuum (QC) method coarse-grains crystalline atomic ensembles in order to bridge the scales from individual atoms to the micro-and mesoscales. A crucial cornerstone of all QC techniques, summation or quadrature rules efficiently approximate the thermodynamic quantities of interest. Here, we investigate summation rules for a fully nonlocal, energy-based QC method to approximate the total Hamiltonian of a crystalline atomic ensemble by a weighted sum over a small subset of all atoms in the crystal lattice. Our formulation does not conceptually differentiate between atomistic and coarsegrained regions and thus allows for seamless bridging without domain-coupling interfaces. We review traditional summation rules and discuss their strengths and weaknesses with a focus on energy approximation errors and spurious force artifacts. Moreover, we introduce summation rules which produce no residual or spurious force artifacts in centrosymmetric crystals in the large-element limit under arbitrary affine deformations in two dimensions (and marginal force artifacts in three dimensions), while allowing us to seamlessly bridge to full atomistics. Through a comprehensive suite of examples with spatially non-uniform QC discretizations in two and three dimensions, we compare the accuracy of the new scheme to various previous ones. Our results confirm that the new summation rules exhibit significantly smaller force artifacts and energy approximation errors. Our numerical benchmark examples include the calculation of elastic constants from completely random QC meshes and the inhomogeneous deformation of aggressively coarse-grained crystals containing nano-voids. In the elastic regime, we directly compare QC results to those of full atomistics to assess global and local errors in complex QC simulations. Going beyond elasticity, we illustrate the performance of the energy-based QC method with the new second-order summation rule by the help of nanoindentation examples with automatic mesh adaptation. Overall, our findings provide guidelines for the selection of summation rules for the fully nonlocal energy-based QC method.

The concurrent bridging of molecular dynamics and continuum thermodynamics presents a number of challenges, mostly associated with energy transmission and changes in the constitutive description of a material across domain boundaries. In this paper, we propose a framework for simulating coarse dynamic systems in the canonical ensemble using the quasicontinuum method (QC). The equations of motion are expressed in reduced QC coordinates and are strictly derived from dissipative Lagrangian mechanics. The derivation naturally leads to a classical Langevin implementation where the timescale is governed by vibrations emanating from the finest length scale occurring in the computational cell. The equations of motion are integrated explicitly via Newmark's (β = 0; γ = 1 2) method, which is parametrized to ensure overdamped dynamics. In this fashion, spurious heating due to reflected vibrations is suppressed, leading to stable canonical trajectories. To estimate the errors introduced by the QC reduction in the resulting dynamics, we have quantified the vibrational entropy losses in Al uniform meshes by calculating the thermal expansion coefficient for a number of conditions. We find that the entropic depletion introduced by coarsening varies linearly with the element size and is independent of the nodal cluster diameter. We rationalize the results in terms of the system, mesh and cluster sizes within the framework of the quasiharmonic approximation. The limitations of the method and alternatives to mitigate the errors introduced by coarsening are discussed. This work represents the first of a series of studies aimed at developing a fully non-equilibrium finite-temperature extension of QC.

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A finite-element turbulent model for the fluid-dynamic and the interfacial mass transfer in gasstirred ladles was developed. The model is based on a dispersed two-phase Eulerian-Eulerian approach and constructs the gas-phase velocity as the liquid velocity plus a gas-liquid slip velocity. In this work, such slip velocity is calculated in terms of the so called ''drift flux model.'' The model is able to describe both desgasification and gas absorption processes in liquid steel systems. The influence of different chemical species was taken into account. Validation was made using experimental data obtained from the literature. These data came from two sources: laboratory and industrial scale tests. The presented model can simulate the turbulent flow pattern and the gas-liquid mass transfer with reasonable accuracy.

A new energy-based quasicontinuum formulation is presented which is based on sampling the crystal energy at carefullychosen lattice sites and which allows for efficiently bridging from the atomistic to the continuum length scale. The presented technique is applied to experiments of nanoindentation whose microstructure-induced size effects can now be studied with full atomistic detail at the micrometer scale without the necessity of phenomenological material models.

SUMMARYThis paper is concerned with the classical problem of wave propagation in discrete models of nonuniform spatial resolution. We develop a new class of Replica Time Integrators (RTIs) that permit the two-way transmission of thermal phonons across mesh interfaces. This two-way transmissibility is accomplished by representing the state of the coarse regions by means of replica ensembles, consisting of collections of identical copies of the coarse regions. In dimension d, RTIs afford an O(n d ) speed-up factor in sequential mode, and O(n d+1 ) in parallel, over regions that are coarsened n-fold. In this work, we restrict ourselves to the solution of the 3d continuous wave equation, for both linear and non-linear materials. By a combination of phase-error analysis and numerical testing, we show that RTIs are convergent and result in exact two-way transmissibility at the Courant-Friedrichs-Lewy limit for any angle of incidence. In this limit, RTIs allow step waves and high-frequency harmonics to cross mesh interfaces in both directions without internal reflections or appreciable loss or addition of energy. The possible connections of RTIs with discrete-to-continuum approaches and, in particular, with the transition between molecular dynamics and continuum thermodynamics are also pointed to by way of future outlook.