A method for the calculation of rate constants from stochastic transition paths.
We present a novel and efficient method for computation of rate constants in the systems where two metastable states are separated by a high free energy barrier. Our approach is based on the thermodynamic integration applied to the grand canonical ensemble of the stochastic transition paths. As illustrated on a multidimensional model system, the required computational costs depend only weakly on the barrier height, which provides a speedup of orders of magnitude in comparison to direct simulations.
Klenin
Konstantin V
KV
Steinbuch Center for Computing, Karlsruhe Institute of Technology, P.O. Box 3640, D-76021 Karlsruhe, Germany.
Wenzel
Wolfgang
W
D003198:Computer Simulation; D007700:Kinetics; D008956:Models, Chemical; D013816:Thermodynamics