Mones, L and Csányi, G (2012) Topologically invariant reaction coordinates for simulating multistate chemical reactions. J Phys Chem B, 116. pp. 14876-14885.Full text not available from this repository.
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.
|Uncontrolled Keywords:||Molecular Dynamics Simulation Quantum Theory Temperature Thermodynamics Water|
|Divisions:||Div C > Applied Mechanics|
|Depositing User:||Cron Job|
|Date Deposited:||18 May 2016 18:05|
|Last Modified:||25 Aug 2016 03:05|