Overcoming barriers in trajectory space: Mechanism and kinetics of rare events via Wang-Landau enhanced transition path sampling

Within the framework of transition path sampling (TPS), activation energies can be computed as path ensemble averages without a priori information about the reaction mechanism [C. Dellago and P. G. Bolhuis, Mol. Simul. 30, 795 (2004)]. Activation energies computed for different conditions can then be used to determine by numerical integration the rate constant for a system of interest from the rate constant known for a reference system. However, in systems with complex potential energy surfaces, multiple reaction pathways may exist making ergodic sampling of trajectory space difficult. Here, we present a combination of TPS with the Wang-Landau (WL) flat-histogram algorithm for an efficient sampling of the transition path ensemble. This method, denoted by WL-TPS, has the advantage that from one single simulation, activation energies at different temperatures can be determined even for systems with multiple reaction mechanisms. The proposed methodology for rate constant calculations does not require the knowledge of the reaction coordinate and is generally applicable to Arrhenius and non-Arrhenius processes. We illustrate the applicability of this technique by studying a two-dimensional toy system consisting of a triatomic molecule immersed in a fluid of repulsive soft disks. We also provide an expression for the calculation of activation volumes from path averages such that the pressure dependence of the rate constant can be obtained by numerical integration. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3496376]