Efficient sampling of atomic configurational spaces.

We describe a method to explore the configurational phase space of chemical systems. It is based on the nested sampling algorithm recently proposed by Skilling (AIP Conf. Proc. 2004, 395; J. Bayesian Anal. 2006, 1, 833) and allows us to explore the entire potential energy surface (PES) efficiently in an unbiased way. The algorithm has two parameters which directly control the trade-off between the resolution with which the space is explored and the computational cost. We demonstrate the use of nested sampling on Lennard-Jones (LJ) clusters. Nested sampling provides a straightforward approximation for the partition function; thus, evaluating expectation values of arbitrary smooth operators at arbitrary temperatures becomes a simple postprocessing step. Access to absolute free energies allows us to determine the temperature-density phase diagram for LJ cluster stability. Even for relatively small clusters, the efficiency gain over parallel tempering in calculating the heat capacity is an order of magnitude or more. Furthermore, by analyzing the topology of the resulting samples, we are able to visualize the PES in a new and illuminating way. We identify a discretely valued order parameter with basins and suprabasins of the PES, allowing a straightforward and unambiguous definition of macroscopic states of an atomistic system and the evaluation of the associated free energies.

Diesel Cylinder Charge Properties: Feed-Forward Control and Cycle-by-Cycle Analysis Using an In-Cylinder Gas Sampling System

Common-rail fuel injection systems on modern light duty diesel engines are effectively able to respond instantaneously to changes in the demanded injection quantity. In contrast, the air-system is subject to significantly slower dynamics, primarily due to filling/emptying effects in the manifolds and turbocharger inertia. The behaviour of the air-path in a diesel engine is therefore the main limiting factor in terms of engine-out emissions during transient operation. This paper presents a simple mean-value model for the air-path during throttled operation, which is used to design a feed-forward controller that delivers very rapid changes in the in-cylinder charge properties. The feed-forward control action is validated using a state-of-the-art sampling system that allows true cycle-by-cycle measurement of the in-cylinder CO2 concentration. © 2011 SAE International.

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.

On the theorem of Reichert

This paper reworks and amplifies Reichert's proof of his theorem (1969) which asserts that any impedance function of a one-port electrical network which can be realised with two reactive elements and an arbitrary number of resistors can be realised with two reactive elements and three resistors. © 2012 Elsevier B.V. All rights reserved.