Comparison of trajectory based methods to find transition states

Abstract

Several trajectory-based methods used to find transition states of a system involving potential energy surfaces, are analyzed. Transition states are in the basin boundaries composed of boundaries of basins of local minima (attractors) of a potential energy surface. Transition states are searched at the basin boundaries in the boundary search method, while in the homotopy method, homotopy trajectory end points automatically lead to transition states. The effectiveness of the boundary search method depends on the selection of a coordinate representation of the system, because geometric structures of basins and basin boundaries depend on this representation. Meanwhile, the homotopy method, which is less sensitive to coordinate representations, successfully finds transition states regardless of coordinate systems.