First-principles energetics of water clusters and ice: a many-body analysis.

Standard forms of density-functional theory (DFT) have good predictive power for many materials, but are not yet fully satisfactory for cluster, solid, and liquid forms of water. Recent work has stressed the importance of DFT errors in describing dispersion, but we note that errors in other parts of the energy may also contribute. We obtain information about the nature of DFT errors by using a many-body separation of the total energy into its 1-body, 2-body, and beyond-2-body components to analyze the deficiencies of the popular PBE and BLYP approximations for the energetics of water clusters and ice structures. The errors of these approximations are computed by using accurate benchmark energies from the coupled-cluster technique of molecular quantum chemistry and from quantum Monte Carlo calculations. The systems studied are isomers of the water hexamer cluster, the crystal structures Ih, II, XV, and VIII of ice, and two clusters extracted from ice VIII. For the binding energies of these systems, we use the machine-learning technique of Gaussian Approximation Potentials to correct successively for 1-body and 2-body errors of the DFT approximations. We find that even after correction for these errors, substantial beyond-2-body errors remain. The characteristics of the 2-body and beyond-2-body errors of PBE are completely different from those of BLYP, but the errors of both approximations disfavor the close approach of non-hydrogen-bonded monomers. We note the possible relevance of our findings to the understanding of liquid water.

Effects of preferential transport in turbulent bluff-body-stabilized lean premixed CH 4/air flames

Preferential species diffusion is known to have important effects on local flame structure in turbulent premixed flames, and differential diffusion of heat and mass can have significant effects on both local flame structure and global flame parameters, such as turbulent flame speed. However, models for turbulent premixed combustion normally assume that atomic mass fractions are conserved from reactants to fully burnt products. Experiments reported here indicate that this basic assumption may be incorrect for an important class of turbulent flames. Measurements of major species and temperature in the near field of turbulent, bluff-body stabilized, lean premixed methane-air flames (Le=0.98) reveal significant departures from expected conditional mean compositional structure in the combustion products as well as within the flame. Net increases exceeding 10% in the equivalence ratio and the carbon-to-hydrogen atom ratio are observed across the turbulent flame brush. Corresponding measurements across an unstrained laminar flame at similar equivalence ratio are in close agreement with calculations performed using Chemkin with the GRI 3.0 mechanism and multi-component transport, confirming accuracy of experimental techniques. Results suggest that the large effects observed in the turbulent bluff-body burner are cause by preferential transport of H 2 and H 2O through the preheat zone ahead of CO 2 and CO, followed by convective transport downstream and away from the local flame brush. This preferential transport effect increases with increasing velocity of reactants past the bluff body and is apparently amplified by the presence of a strong recirculation zone where excess CO 2 is accumulated. © 2011 The Combustion Institute.

The rise heights of low-and high-Froude-number turbulent axisymmetric fountains

We present the results of an experimental investigation across a broad range of source Froude numbers, 0. 4 ≤ Fr 0 ≤ 45, into the dynamics, morphology and rise heights of Boussinesq turbulent axisymmetric fountains in quiescent uniform environments. Typically, these fountains are thought to rise to an initial height, z i, before settling back and fluctuating about a lesser (quasi-) steady height, z ss. Our measurements show that this is not always the case and the ratio of the fountain's initial rise height to steady rise height, λ = z i/z ss, varies widely, 0. 5 ≈ λ ≈ 2, across the range of Fr 0 investigated. As a result of near-ideal start-up conditions provided by the experimental set-up we were consistently able to form a vortex at the fountain's front. This enabled new insights into two features of the initial rise of turbulent fountains. Firstly, for 1. 0 ≈ Fr 0 ≈ 1. 7 the initial rise height is less than the steady rise height. Secondly, for Fr 0 ≈ 5. 5, the vortex formed at the fountain's front pinches off, separates from the main body and rises high above the fountain; there is thus a third rise height to consider, namely, the maximum vortex rise height, z v. From our observations we propose classifying turbulent axisymmetric fountains into five regimes (as opposed to the current three regimes) and present detailed descriptions of the flow in each. Finally, based on an analysis of the rise height fluctuations and the width of fountains in (quasi-) steady state we provide further insight into the physical cause of height fluctuations. © 2011 Cambridge University Press.

Flow field measurements of a series of turbulent premixed and stratified methane/air flames

This paper presents flow field measurements for the turbulent stratified burner introduced in two previous publications in which high resolution scalar measurements were made by Sweeney et al. [1,2] for model validation. The flow fields of the series of premixed and stratified methane/air flames are investigated under turbulent, globally lean conditions (φg=0.75). Velocity data acquired with laser Doppler anemometry (LDA) and particle image velocimetry (PIV) are presented and discussed. Pairwise 2-component LDA measurements provide profiles of axial velocity, radial velocity, tangential velocity and corresponding fluctuating velocities. The LDA measurements of axial and tangential velocities enable the swirl number to be evaluated and the degree of swirl characterized. Power spectral density and autocorrelation functions derived from the LDA data acquired at 10kHz are optimized to calculate the integral time scales. Flow patterns are obtained using a 2-component PIV system operated at 7Hz. Velocity profiles and spatial correlations derived from the PIV and LDA measurements are shown to be in very good agreement, thus offering 3D mapping of the velocities. A strong correlation was observed between the shape of the recirculation zones above the central bluff body and the effects of heat release, stoichiometry and swirl. Detailed analyses of the LDA data further demonstrate that the flow behavior changes significantly with the levels of swirl and stratification, which combines the contributions of dilatation, recirculation and swirl. Key turbulence parameters are derived from the total velocity components, combining axial, radial and tangential velocities. © 2013 The Combustion Institute.