Efficiency analysis of reaction rate calculation methods using analytical models I: The two-dimensional sharp barrier.
We analyze the efficiency of different methods for the calculation of reaction rates in the case of a simple two-dimensional analytical benchmark system. Two classes of methods are considered: the first is based on the free energy calculation along a reaction coordinate and the calculation of the transmission coefficient, the second on the sampling of dynamical pathways. We give scaling rules for how this efficiency depends on barrier height and width, and we hand out simple optimization rules for the method-specific parameters. We show that the path sampling methods, using the transition interface sampling technique, become exceedingly more efficient than the others when the reaction coordinate is not the optimal one.
van Erp
Titus S
TS
Centrum voor Oppervlaktechemie en Katalyse, K.U. Leuven, Kasteelpark Arenberg 23, B-3001 Leuven, Belgium. titus.vanerp@biw.kuleuven.be
D000465:Algorithms; D003198:Computer Simulation; D007700:Kinetics; D008956:Models, Chemical; D011789:Quantum Theory; D013816:Thermodynamics