Why are Fluid Densities So Low in Carbon Nanotubes?

The equilibrium density of fluids under nanoconfinement can differ substantially from their bulk density. Using a mean-field approach to describe the energetic landscape near the carbon nanotube (CNT) wall, we obtain analytical results describing the lengthscales associated with the layering observed at the fluid-CNT interface. When combined with molecular simulation results for the fluid density in the layered region, this approach allows us to derive a closed-form prediction for the overall equilibrium fluid density as a function of the CNT radius that is in excellent agreement with molecular dynamics simulations. We also show how aspects of this theory can be extended to describe water confined within CNTs and find good agreement with results from the literature

A Universal Molecular-Kinetic Scaling Relation for Slip of a Simple Fluid at a Solid Boundary

Using the observation that slip in simple fluids at low and moderate shear rates is a thermally activated process driven by the shear stress in the fluid close to the solid boundary, we develop a molecular-kinetic model for simple fluid slip at solid boundaries. The proposed model, which is in the form of a universal scaling relation that connects slip and shear rate, reduces to the well known Navier-slip condition under low shear conditions, providing a direct connection between molecular parameters and the slip length. Molecular-dynamics simulations are in very good agreement with the predicted dependence of slip on system parameters, including the temperature and fluid-solid interaction strength. Connections between our model and previous work, as well as simulation and experimental results are explored and discussed

Gas-flow animation by unsteady heating in a microchannel

We study the flow-field generated in a one-dimensional wall-bounded gas layer due to an arbitrary small-amplitude time variation in the temperature of its boundaries. Using the Fourier transform technique, analytical results are obtained for the slip-flow/Navier–Stokes limit. These results are complemented by low-variance simulations of the Boltzmann equation, which are useful for establishing the limits of the slip-flow description, as well as for bridging the gap between the slip-flow analysis and previously developed free-molecular analytical predictions. Results are presented for both periodic (sinusoidal) and nonperiodic (step-jump) heating profiles. Our slip-flow solution is used to elucidate a singular limit reported in the literature for oscillatory heating of a dynamically incompressible fluid

Modeling the Electrophoretic Separation of Short Biological Molecules in Nanofluidic Devices

Via comparisons with rigid-rod and wormlike-chain Brownian dynamics (BD) simulations and the experimental results of Fu et al. (2006, “Molecular Sieving in Periodic Free-Energy Landscapes Created by Patterned Nanofilter Arrays,” Phys. Rev. Lett., 97(1), p. 018103), we demonstrate that, for the purposes of low-to-medium field electrophoretic separation, sufficiently short biomolecules can be modeled as point particles, with their orientational degrees of freedom accounted for using partition coefficients. This observation is used in the present work to build an efficient BD simulation method. Particular attention is paid to the model's ability to quantitatively capture experimental results using realistic values of all physical parameters

Steepest Entropy Ascent Models of the Boltzmann Equation: Comparisons With Hard-Sphere Dynamics and Relaxation-Time Models for Homogeneous Relaxation From Highly Non-Equilibrium States

We present a family of steepest entropy ascent (SEA) models of the Boltzmann equation. The models preserve the usual collision invariants (mass, momentum, energy), as well as the non-negativity of the phase-space distribution, and have a strong built-in thermodynamic consistency, i.e., they entail a general H-theorem valid even very far from equilibrium. This family of models features a molecular-speed-dependent collision frequency; each variant can be shown to approach a corresponding BGK model with the same variable collision frequency in the limit of small deviation from equilibrium. This includes power-law dependence on the molecular speed for which the BGK model is known to have a Prandtl number that can be adjusted via the power-law exponent. We compare numerical solutions of the constant and velocity-dependent collision frequency variants of the SEA model with the standard relaxation-time model and a Monte Carlo simulation of the original Boltzmann collision operator for hard spheres for homogeneous relaxation from near-equilibrium and highly non-equilibrium states. Good agreement is found between all models in the near-equilibrium regime. However, for initial states that are far from equilibrium, large differences are found; this suggests that the maximum entropy production statistical ansatz is not equivalent to Boltzmann collisional dynamics and needs to be modified or augmented via additional constraints or structure.Fondazione Caripl

Long range correction for wall-fluid interaction in molecular dynamic simulations

A new method is proposed for correctly modeling the long range interaction between a fluid and a bounding wall in atomistic simulations. This method incorporates the molecular structure of the solid substrate while allowing for a finite interaction cutoff by making a proper estimation of long range correction for the fluid-wall interaction. The method is then applied to a molecular dynamic simulation of a spreading droplet. Conparison to simulations using several other previously used methods shows that the long range correction can be significant in some circumstances.Singapore-MIT Alliance (SMA

Simulation of Heat Transport in Graphene Nanoribbons Using the Ab-Initio Scattering Operator

We present a deviational Monte Carlo method for simulating phonon transport in graphene using the ab initio 3-phonon scattering operator. This operator replaces the commonly used relaxation-time approximation, which is known to neglect, among other things, coupling between out of equilibrium states that are particularly important in graphene. Phonon dispersion relations and transition rates are obtained from density functional theory calculations. The proposed method provides, for the first time, means for obtaining solutions of the Boltzmann transport equation with ab initio scattering for time- and spatially-dependent problems. The deviational formulation ensures that simulations are computationally feasible for arbitrarily small temperature differences; within this formulation, the ab initio scattering operator is treated using an efficient stochastic algorithm which, in the limit of large number of states, outperforms the more traditional deterministic methods used in solutions of the homogeneous Boltzmann equation. We use the proposed method to study heat transport in graphene ribbons.National Science Foundation (U.S.). Graduate Research Fellowship ProgramAmerican Society for Engineering Education. National Defense Science and Engineering Graduate FellowshipSingapore-MIT Allianc

Reconstruction of phonon relaxation times from systems featuring interfaces with unknown properties

We present a method for reconstructing the phonon relaxation-time function τ[subscript ω]=τ(ω) (including polarization) and associated phonon free-path distribution from thermal spectroscopy data for systems featuring interfaces with unknown properties. Our method does not rely on the effective thermal-conductivity approximation or a particular physical model of the interface behavior. The reconstruction is formulated as an optimization problem in which the relaxation times are determined as functions of frequency by minimizing the discrepancy between the experimentally measured temperature profiles and solutions of the Boltzmann transport equation for the same system. Interface properties such as transmissivities are included as unknowns in the optimization; however, because for the thermal spectroscopy problems considered here the reconstruction is not very sensitive to the interface properties, the transmissivities are only approximately reconstructed and can be considered as byproducts of the calculation whose primary objective is the accurate determination of the relaxation times. The proposed method is validated using synthetic experimental data obtained from Monte Carlo solutions of the Boltzmann transport equation. The method is shown to remain robust in the presence of uncertainty (noise) in the measurement