Bridging length and time scales in sheared demixing systems: from the Cahn-Hilliard to the Doi-Ohta model

We develop a systematic coarse-graining procedure which establishes the connection between models of mixtures of immiscible fluids at different length and time scales. We start from the Cahn-Hilliard model of spinodal decomposition in a binary fluid mixture under flow from which we derive the coarse-grained description. The crucial step in this procedure is to identify the relevant coarse-grained variables and find the appropriate mapping which expresses them in terms of the more microscopic variables. In order to capture the physics of the Doi-Ohta level, we introduce the interfacial width as an additional variable at that level. In this way, we account for the stretching of the interface under flow and derive analytically the convective behavior of the relevant coarse-grained variables, which in the long wavelength limit recovers the familiar phenomenological Doi-Ohta model. In addition, we obtain the expression for the interfacial tension in terms of the Cahn-Hilliard parameters as a direct result of the developed coarse-graining procedure. Finally, by analyzing the numerical results obtained from the simulations on the Cahn-Hilliard level, we discuss that dissipative processes at the Doi-Ohta level are of the same origin as in the Cahn-Hilliard model. The way to estimate the interface relaxation times of the Doi-Ohta model from the underlying morphology dynamics simulated at the Cahn-Hilliard level is established.Comment: 29 pages, 2 figures, accepted for publication in Phys. Rev.

The geometry and thermodynamics of dissipative quantum systems

Dirac's method of classical analogy is employed to incorporate quantum degrees of freedom into modern nonequilibrium thermodynamics. The proposed formulation of dissipative quantum mechanics builds entirely upon the geometric structures implied by commutators and canonical correlations. A lucid formulation of a nonlinear quantum master equation follows from the thermodynamic structure. Complex classical environments with internal structure can be handled readily.Comment: 4 pages, definitely no figure

Stochastic process behind nonlinear thermodynamic quantum master equation

We propose a piecewise deterministic Markovian jump process in Hilbert space such that the covariance matrix of this stochastic process solves the thermodynamic quantum master equation. The proposed stochastic process is particularly simple because the normalization of the vectors in Hilbert space is preserved only on average. As a consequence of the nonlinearity of the thermodynamic master equation, the construction of stochastic trajectories involves the density matrix as a running ensemble average. We identify a principle of detailed balance and a fluctuation-dissipation relation for our Markovian jump process.Comment: 4 page

Rouse Chains with Excluded Volume Interactions: Linear Viscoelasticity

Linear viscoelastic properties for a dilute polymer solution are predicted by modeling the solution as a suspension of non-interacting bead-spring chains. The present model, unlike the Rouse model, can describe the solution's rheological behavior even when the solvent quality is good, since excluded volume effects are explicitly taken into account through a narrow Gaussian repulsive potential between pairs of beads in a bead-spring chain. The use of the narrow Gaussian potential, which tends to the more commonly used delta-function repulsive potential in the limit of a width parameter "d" going to zero, enables the performance of Brownian dynamics simulations. The simulations results, which describe the exact behavior of the model, indicate that for chains of arbitrary but finite length, a delta-function potential leads to equilibrium and zero shear rate properties which are identical to the predictions of the Rouse model. On the other hand, a non-zero value of "d" gives rise to a prediction of swelling at equilibrium, and an increase in zero shear rate properties relative to their Rouse model values. The use of a delta-function potential appears to be justified in the limit of infinite chain length. The exact simulation results are compared with those obtained with an approximate solution which is based on the assumption that the non-equilibrium configurational distribution function is Gaussian. The Gaussian approximation is shown to be exact to first order in the strength of excluded volume interaction, and is found to be accurate above a threshold value of "d", for given values of chain length and strength of excluded volume interaction.Comment: Revised version. Long chain limit analysis has been deleted. An improved and corrected examination of the long chain limit will appear as a separate posting. 32 pages, 9 postscript figures, LaTe

Thermodynamically admissible form for discrete hydrodynamics

We construct a discrete model of fluid particles according to the GENERIC formalism. The model has the form of Smoothed Particle Hydrodynamics including correct thermal fluctuations. A slight variation of the model reproduces the Dissipative Particle Dynamics model with any desired thermodynamic behavior. The resulting algorithm has the following properties: mass, momentum and energy are conserved, entropy is a non-decreasing function of time and the thermal fluctuations produce the correct Einstein distribution function at equilibrium.Comment: 4 page

Inconsistency of a dissipative contribution to the mass flux in hydrodynamics

The possibility of dissipative contributions to the mass flux is considered in detail. A general, thermodynamically consistent framework is developed to obtain such terms, the compatibility of which with general principles is then checked--including Galilean invariance, the possibility of steady rigid rotation and uniform center-of-mass motion, the existence of a locally conserved angular momentum, and material objectivity. All previously discussed scenarios of dissipative mass fluxes are found to be ruled out by some combinations of these principles, but not a new one that includes a smoothed velocity field v-bar. However, this field v-bar is nonlocal and leads to unacceptable consequences in specific situations. Hence we can state with confidence that a dissipative contribution to the mass flux is not possible.Comment: 18 pages; submitted to Phys. Rev.

Thermodynamically guided nonequilibrium Monte Carlo method for generating realistic shear flows in polymeric systems

A thermodynamically guided atomistic MonteCarlo methodology is presented for simulating systems beyond equilibrium by expanding the statistical ensemble to include a tensorial variable accounting for the overall structure of the system subjected to flow. For a given shear rate, the corresponding tensorial conjugate field is determined iteratively through independent nonequilibrium molecular dynamics simulations. Test simulations for the effect of flow on the conformation of a C50H102 polyethylene liquid show that the two methods (expanded MonteCarlo and nonequilibrium molecular dynamics) provide identical results.open181

Analysis of the thermomechanical inconsistency of some extended hydrodynamic models at high Knudsen number

There are some hydrodynamic equations that, while their parent kinetic equation satisfies fundamental mechanical properties, appear themselves to violate mechanical or thermodynamic properties. This article aims to shed some light on the source of this problem. Starting with diffusive volume hydrodynamic models, the microscopic temporal and spatial scales are first separated at the kinetic level from the macroscopic scales at the hydrodynamic level. Then we consider Klimontovich’s spatial stochastic version of the Boltzmann kinetic equation, and show that, for small local Knudsen numbers, the stochastic term vanishes and the kinetic equation becomes the Boltzmann equation. The collision integral dominates in the small local Knudsen number regime, which is associated with the exact traditional continuum limit. We find a sub-domain of the continuum range which the conventional Knudsen number classification does not account for appropriately. In this sub-domain, it is possible to obtain a fully mechanically-consistent volume (or mass) diffusion model that satisfies the second law of thermodynamics on the grounds of extended non-local-equilibrium thermodynamics

Polymers in linear shear flow: a numerical study

We study the dynamics of a single polymer subject to thermal fluctuations in a linear shear flow. The polymer is modeled as a finitely extendable nonlinear elastic FENE dumbbell. Both orientation and elongation dynamics are investigated numerically as a function of the shear strength, by means of a new efficient integration algorithm. The results are in agreement with recent experiments.Comment: 7 pages, see also the preceding paper (http://arxiv.org/nlin.CD/0503028