Alan J. H. McGaughey

Reassessing Fast Water Transport Through Carbon Nanotubes

Pressure-driven water flow through carbon nanotubes (CNTs) with diameters ranging from 1.66 to 4.99 nm is examined using molecular dynamics simulation. The flow rate enhancement, defined as the ratio of the observed flow rate to that predicted from the no-slip Hagen-Poiseuille relation, is calculated for each CNT. The enhancement decreases with increasing CNT diameter and ranges from 433 to 47. By calculating the variation of water viscosity and slip length as a function of CNT diameter, it is found that the results can be fully explained in the context of continuum fluid mechanics. The enhancements are lower than previously reported experimental results, which range from 560 to 100 000, suggesting a miscalculation of the available flow area and/or the presence of an uncontrolled external driving force (such as an electric field) in the experiments.

Broadband phonon mean free path contributions to thermal conductivity measured using frequency domain thermoreflectance

Non-metallic crystalline materials conduct heat by the transport of quantized atomic lattice vibrations called phonons. Thermal conductivity depends on how far phonons travel between scattering events-their mean free paths. Due to the breadth of the phonon mean free path spectrum, nanostructuring materials can reduce thermal conductivity from bulk by scattering long mean free path phonons, whereas short mean free path phonons are unaffected. Here we use a breakdown in diffusive phonon transport generated by high-frequency surface temperature modulation to identify the mean free path-dependent contributions of phonons to thermal conductivity in crystalline and amorphous silicon. Our measurements probe a broad range of mean free paths in crystalline silicon spanning 0.3-8.0 μm at a temperature of 311 K and show that 40±5% of its thermal conductivity comes from phonons with mean free path >1 μm. In a 500 nm thick amorphous silicon film, despite atomic disorder, we identify propagating phonon-like modes that contribute >35±7% to thermal conductivity at a temperature of 306 K.

Strongly anisotropic in-plane thermal transport in single-layer black phosphorene

Using first principles calculations, we predict the thermal conductivity of the two-dimensional materials black phosphorene and blue phosphorene. Black phosphorene has an unprecedented thermal conductivity anisotropy ratio of three, with predicted values of 110 W/m-K and 36 W/m-K along its armchair and zigzag directions at a temperature of 300 K. For blue phosphorene, which is isotropic with a zigzag structure, the predicted value is 78 W/m-K. The two allotropes show strikingly different thermal conductivity accumulation, with phonons of mean free paths between 10 nm and 1 μm dominating in black phosphorene, while a much narrower band of mean free paths (50–200 nm) dominate in blue phosphorene. Black phosphorene shows intriguing potential for strain-tuning of its thermal conductivity tensor.

Phonon Transport in Molecular Dynamics Simulations: Formulation and Thermal Conductivity Prediction

Publisher Summary This chapter discusses the phonon transport in molecular dynamics (MD) simulations. The chapter presents a formulation for studying the thermal transport in dielectric materials using MD simulations. The simulations allow for analysis in both the real and phonon spaces. The natural inclusion of anharmonic effects through the form of the interatomic potential presents a significant advantage over harmonic theories. The chapter describes, examines, and compares two major approaches for predicting thermal conductivity from MD simulations (the Green–Kubo method [GK] and direct methods). Each has advantages and disadvantages, and the method chosen strongly depends on the problem of interest. Generally, the GK method is superior for bulk phase simulations, while the direct method is best for finite structures. In terms of applying MD simulations to real systems, current computational resources cannot accurately model anything close to a micron in size on an atom-by-atom level. The upscaling of MD results to larger length scale models is a promising and exciting avenue. Upscaling has been applied in a different context to phonon transport across material interfaces by Schelling and Phillpot.

Surface chemistry mediates thermal transport in three-dimensional nanocrystal arrays

Arrays of ligand-stabilized colloidal nanocrystals with size-tunable electronic structure are promising alternatives to single-crystal semiconductors in electronic, optoelectronic and energy-related applications. Hard/soft interfaces in these nanocrystal arrays (NCAs) create a complex and uncharted vibrational landscape for thermal energy transport that will influence their technological feasibility. Here, we present thermal conductivity measurements of NCAs (CdSe, PbS, PbSe, PbTe, Fe3O4 and Au) and reveal that energy transport is mediated by the density and chemistry of the organic/inorganic interfaces, and the volume fractions of nanocrystal cores and surface ligands. NCA thermal conductivities are controllable within the range 0.1-0.3 W m(-1) K(-1), and only weakly depend on the thermal conductivity of the inorganic core material. This range is 1,000 times lower than the thermal conductivity of silicon, presenting challenges for heat dissipation in NCA-based electronics and photonics. It is, however, 10 times smaller than that of Bi2Te3, which is advantageous for NCA-based thermoelectric materials.

In-plane phonon transport in thin films

The in-plane phonon thermal conductivities of argon and silicon thin films are predicted from the Boltzmann transport equation under the relaxation time approximation. We model the thin films using bulk phonon properties obtained from harmonic and anharmonic lattice dynamics calculations. The input required for the lattice dynamics calculations is obtained from interatomic potentials: Lennard-Jones for argon and Stillinger–Weber for silicon. The effect of the boundaries is included by considering only phonons with wavelengths that fit within the film and adjusting the relaxation times to account for mode-dependent, diffuse boundary scattering. Our model does not rely on the isotropic approximation or any fitting parameters. For argon films thicker than 4.3 nm and silicon films thicker than 17.4 nm, the use of bulk phonon properties is found to be appropriate and the predicted reduction in the in-plane thermal conductivity is in good agreement with results obtained from molecular dynamics simulation and ex...

Cross-plane phonon transport in thin films

We predict the cross-plane phonon thermal conductivity of Stillinger-Weber silicon thin films as thin as 17.4 nm using the lattice Boltzmann method. The thin films are modeled using bulk phonon properties obtained from harmonic and anharmonic lattice dynamics calculations. We use this approach, which considers all of the phonons in the first Brillouin-zone, to assess the suitability of common assumptions. Specifically, we assess the validity of: (i) neglecting the contributions of optical modes, (ii) the isotropic approximation, (iii) assuming an averaged bulk mean-free path, and (iv) the Matthiessen rule. Because the frequency-dependent contributions to thermal conductivity change as the film thickness is reduced, assumptions that are valid for bulk are not necessarily valid for thin films.

Size-dependent model for thin film and nanowire thermal conductivity

We present an analytical model for the size-dependence of thin film and nanowire thermal conductivity and compare the predictions to experimental measurements on silicon nanostructures. The model contains no fitting parameters and only requires the bulk lattice constant, bulk thermal conductivity, and an acoustic phonon speed as inputs. By including the mode-dependence of the phonon lifetimes resulting from phonon-phonon and phonon-boundary scattering, the model captures the approach to the bulk thermal conductivity of the experimental data better than gray models based on a single lifetime.

Density, distribution, and orientation of water molecules inside and outside carbon nanotubes

The behavior of water molecules inside and outside 1.1, 2.8, 6.9, and 10.4 nm diameter armchair carbon nanotubes (CNTs) is predicted using molecular dynamics simulations. The effects of CNT diameter on mass density, molecular distribution, and molecular orientation are identified for both the confined and unconfined fluids. Within 1 nm of the CNT surface, unconfined water molecules assume a spatially varying density profile. The molecules distribute nonuniformly around the carbon surface and have preferred orientations. The behavior of the unconfined water molecules is invariant with CNT diameter. The behavior of the confined water, however, can be correlated to tube diameter. Inside the 10.4 nm CNT, the molecular behavior is indistinguishable from that of the unconfined fluid. Within the smaller CNTs, surface curvature effects reduce the equilibrium water density and force water molecules away from the surface. This effect changes both the molecular distribution and preferred molecular orientations.

Phonon band structure and thermal transport correlation in a layered diatomic crystal

To elucidate the three-way relationship among a crystal’s structure, its phonon dispersion characteristics, and its thermal conductivity, an analysis is conducted on layered diatomic Lennard-Jones crystals with various mass ratios. Lattice dynamics theory and molecular dynamics simulations are used to predict the phonon dispersion curves and the thermal conductivity. The layered structure generates directionally dependent thermal conductivities lower than those predicted by density trends alone. The dispersion characteristics are quantified using a set of band diagram metrics, which are used to assess the contributions of acoustic phonons and optical phonons to the thermal conductivity. The thermal conductivity increases as the extent of the acoustic modes increases, and it decreases as the extent of the stop bands increases. The sensitivity of the thermal conductivity to the band diagram metrics is highest at low temperatures, where there is less anharmonic scattering, indicating that dispersion plays a more prominent role in thermal transport in that regime. We propose that the dispersion metrics i provide an indirect measure of the relative contributions of dispersion and anharmonic scattering to the thermal transport, and ii uncouple the standard thermal conductivity structure-property relation to that of structure-dispersion and dispersion-property relations, providing opportunities for better understanding of the underlying physical mechanisms and a potential tool for material design.