Topologically invariant reaction coordinates for simulating multistate chemical reactions.

Evaluating free energy profiles of chemical reactions in complex environments such as solvents and enzymes requires extensive sampling, which is usually performed by potential of mean force (PMF) techniques. The reliability of the sampling depends not only on the applied PMF method but also the reaction coordinate space within the dynamics is biased. In contrast to simple geometrical collective variables that depend only on the positions of the atomic coordinates of the reactants, the E(gap) reaction coordinate (the energy difference obtained by evaluating a suitable force field using reactant and product state topologies) has the unique property that it is able to take environmental effects into account leading to better convergence, a more faithful description of the transition state ensemble and therefore more accurate free energy profiles. However, E(gap) requires predefined topologies and is therefore inapplicable for multistate reactions, in which the barrier between the chemically equivalent topologies is comparable to the reaction activation barrier, because undesired "side reactions" occur. In this article, we introduce a new energy-based collective variable by generalizing the E(gap) reaction coordinate such that it becomes invariant to equivalent topologies and show that it yields more well behaved free energy profiles than simpler geometrical reaction coordinates.

Fracture mechanics of idealised bituminous mixes

© 2014 Taylor & Francis. The durability of asphalt pavements is strongly impaired by cracks, caused primarily by traffic loads and environmental effects. In this work, fracture behaviour of idealised asphalt mixes is investigated. Experiments on idealised asphalt mixes under pure-tension mode (mode I cracking) were performed and fracture parameters were evaluated. In these three-point bend fracture tests, the test variables were temperature and load rate. The test data were stored in an asphalt materials database and special-purpose tools were implemented to analyse and handle the laboratory data automatically. Fracture mechanism maps were constructed, showing the conditions associated with ductile, brittle and ductile-brittle transition regimes of behaviour. The mechanism maps show the failure response of the material in terms of the stress intensity factor, strain energy release rate and J-integral as a function of the temperature-compensated crack mouth opening strain rate. Fracture behaviour of asphalt mix specimens was simulated by cohesive zone model in conjunction with a novel material constitutive model for asphalt mixes. The finite element model agrees well with the experimental results and provides insights into fracture response of the notched asphalt mix beam specimens.

Electroluminescence analysis and simulation of the effects of injection and temperature on carrier distribution in InGaN-based light-emitting diodes with color-coded quantum wells

This paper reports on an extensive analysis of the electroluminescence characteristics of InGaN-based LEDs with color-coded structure, i.e., with a triple quantum well structure in which each quantum well has a different indium content. The analysis is based on combined electroluminescence measurements and two-dimensional simulations, carried out at different current and temperature levels. Results indicate that (i) the efficiency of each of the quantum wells strongly depends on device operating conditions (current and temperature); (ii) at low current and temperature levels, only the quantum well closer to the p-side has a significant emission; (iii) emission from the other quantum wells is favored at high current levels. The role of carrier injection, hole mobility, carrier density and non-radiative recombination in determining the relative intensity of the quantum wells is discussed in the text. © 2013 The Japan Society of Applied Physics.