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.

Manufacturing dish shaped rings on radial-axial ring rolling mills

Ring rolling is an established method to produce seamless rings of different cross-sectional geometries. For dish shaped rings, there are applications in different areas such as offshore, aeronautics or the energy sector. At the moment, dish shaped rings are produced by machining of rings with rectangular shaped cross section, by (open die) hollow forging on a conical mandrel or by using shaped ring rolling tools. These ways of manufacturing have the disadvantage of high material waste, additional costs for special tools, long process time and limited or inflexible geometries. Therefore, the manufacturing of dish shaped rings on conventional radial-axial ring rolling mills would expand the range of products for ring producers. The aim of this study is to investigate the feasibility of an alternative to the current manufacturing processes, without requiring additional tooling and material costs. Therefore, the intended formation of dish shaped rings-previously regarded as a form error-is investigated. Based on an analysis of geometrical requirements and metal flow mechanisms, a rolling strategy is presented, causing dishing and ring climbing by a large height reduction of the ring. Using this rolling strategy dish shaped rings with dishing angles up to 18° were achieved. In addition to the experiments finite element method (FEM)-simulations of the process have been successfully conducted, in order to analyze the local strain evolution. However, when the contact between ring and main roll is lost in the process the ring starts to oscillate around the mandrel and neither dishing nor ring climbing is observed. © 2013 German Academic Society for Production Engineering (WGP).