Nested sampling for materials: the case of hard spheres

The recently introduced nested sampling algorithm allows the direct and efficient calculation of the partition function of atomistic systems. We demonstrate its applicability to condensed phase systems with periodic boundary conditions by studying the three dimensional hard sphere model. Having obtained the partition function, we show how easy it is to calculate the compressibility and the free energy as functions of the packing fraction and local order, verifying that the transition to crystallinity has a very small barrier, and that the entropic contribution of jammed states to the free energy is negligible for packing fractions above the phase transition. We quantify the previously proposed schematic phase diagram and estimate the extent of the region of jammed states. We find that within our samples, the maximally random jammed configuration is surprisingly disordered.

The geometry and the number of contacts of monodisperse sphere packs using X-ray tomography

The three-dimensional structure of very large samples of monodisperse bead packs is studied by means of X-Ray Computed Tomography. We retrieve the coordinatesofeach bead inthe pack and wecalculate the average coordination number by using the tomographic images to single out the neighbors in contact. The results are compared with the average coordination number obtained in Aste et al. (2005) by using a deconvolution technique. We show that the coordination number increases with the packing fraction, varying between 6.9 and 8.2 for packing fractions between 0.59 and 0.64. © 2005 Taylor & Francis Group.

Twisting transition between crystalline and fibrillar phases of aggregated peptides

We study two distinctly ordered condensed phases of polypeptide molecules, amyloid fibrils and amyloidlike microcrystals, and the first-order twisting phase transition between these two states. We derive a single free-energy form which connects both phases. Our model identifies relevant degrees of freedom for describing the collective behavior of supramolecular polypeptide structures, reproduces accurately the results from molecular dynamics simulations as well as from experiments, and sheds light on the uniform nature of the dimensions of different peptide fibrils. © 2012 American Physical Society.

On the transition from finite-volume negatively buoyant releases to continuous fountains

An experimental investigation to identify the source conditions that distinguish finite-volume negatively buoyant fluid projectile behaviour from fountain behaviour in quiescent environments of uniform density is described. Finite-volume releases are governed by their source Froude number Fr D and the aspect ratio L/D of the release, where L denotes the length of the column of fluid dispensed vertically from the nozzle of diameter D. We establish the influence of L/D on the peak rise heights of a release formed by dispensing saline solution into fresh water for 0

Aromaticity on the fly: cyclic transition state stabilization at finite temperature.

We study the transition state of pericyclic reactions at elevated temperature with unbiased ab initio molecular dynamics. We find that the transition state of the intramolecular rearrangements for barbaralane and bullvalene remains aromatic at high temperature despite the significant thermal atomic motions. Structural, magnetic, and electronic properties of the dynamical transition state show the concertedness and aromatic character. Free-energy calculations also support the validity of the transition state theory for the present rearrangement reactions. The calculations demonstrate that cyclic delocalization represents a strong force to synchronize the thermal atomic motions even at high temperatures.

Accurate screened exchange band structures for the transition metal monoxides MnO, FeO, CoO and NiO.

We report calculations of the band structures and density of states of the four transition metal monoxides MnO, FeO, CoO and NiO using the hybrid density functional sX-LDA ('screened exchange local density approximation'). Late transition metal oxides are prototypical examples of strongly correlated materials, which pose challenges for electronic structure methods. We compare our results with available experimental data and show that our calculations generally yield accurate predictions for the fundamental band gaps and valence bands, in favourable agreement with previously reported theoretical studies. For MnO, the band gaps are still underestimated, suggesting additional many-body effects that are not captured by our screened hybrid functional approach.

A fast detailed-chemistry modelling approach for simulating the SI-HCCI transition

An established Stochastic Reactor Model (SRM) is used to simulate the transition from Spark Ignition (SI) to Homogeneous Charge Compression Ignition (HCCI) combustion mode in a four cylinder in-line four-stroke naturally aspirated direct injection SI engine with cam profile switching. The SRM is coupled with GT-Power, a one-dimensional engine simulation tool used for modelling engine breathing during the open valve portion of the engine cycle, enabling multi-cycle simulations. The mode change is achieved by switching the cam profiles and phasing, resulting in a Negative Valve Overlap (NVO), opening the throttle, advancing the spark timing and reducing the fuel mass as well as using a pilot injection. A proven technique for tabulating the model is used to create look-up tables in both SI and HCCI modes. In HCCI mode several tables are required, including tables for the first NVO, transient valve timing NVO, transient valve timing HCCI and steady valve timing HCCI and NVO. This results in the ability to simulate the transition with detailed chemistry in very short computation times. The tables are then used to optimise the transition with the goal of reducing NO x emissions and fluctuations in IMEP. Copyright © 2010 SAE International.

A detailed chemistry simulation of the SI-HCCI transition

A Stochastic Reactor Model (SRM) has been used to simulate the transition from Spark Ignition (SI) mode to Homogeneous Charge Compression Ignition (HCCI) mode in a four cylinder in-line four-stroke naturally aspirated direct injection SI engine with cam profile switching. The SRM is coupled with GT-Power, a one-dimensional engine simulation tool used for modelling engine breathing during the open valve portion of the engine cycle, enabling multi-cycle simulations. The model is initially calibrated in both modes using steady state data from SI and HCCI operation. The mode change is achieved by switching the cam profiles and phasing, resulting in a Negative Valve Overlap (NVO), opening the throttle, advancing the spark timing and reducing the fuel mass as well as utilising a pilot injection. Experimental data is presented along with the simulation results. The model is used to investigate key control parameters and their effects on parameters that are difficult to measure experimentally. The effect of the spark in the first HCCI cycles is found to have a major impact on the stability of the transition. Copyright © 2010 SAE International.