Unprejudiced identification of reaction mechanisms from biased transition path sampling.

A method for unprejudiced investigation of reaction mechanisms from molecular-dynamics simulations is presented. It combines the transition path sampling approach with a biasing strategy, which (a) allows optimization of transition paths crossing an energy minimum of the transition state surface. The bias is then used to (b) find reaction pathways, which follow different mechanistic routes. In the first step the manifold of similar trajectories that correspond to the same mechanism is reduced to a single characteristic dynamical path. Our method then allows a systematic search for further reaction mechanisms and the related energy barriers. It is illustrated at the example of a single particle in a two-dimensional potential and of the rather complex process of the pressure-induced insertion of a helium atom into a C60 buckyball molecule.