Heuristic control of kinetic energy in dynamic reaction coordinate calculations

Abstract

For the understanding and prediction of chemical reactions, detailed knowledge of the minimum energy path between reactants and transition state is of utmost importance. Stewart et al. (J. Comput. Chem. 1987, 8, 1117) proposed the usage of molecular trajectories calculated from Newton's equations of motion for an efficient reaction path following. Two operational modes are possible thereby: intrinsic (IRC) and dynamic reaction coordinate calculations (DRC). The technical difference between these modes is that in an IRC calculation the kinetic energy of the nuclei is quenched while the total energy is conserved in DRC calculations. In this work, a heuristic control methodology of atomic kinetic energies in DRC calculations using fuzzy logic is proposed. A diversified test set of 10 reactions has been collected to examine the performance of this approach. Fuzzy rule-based models are found to be a convenient way to make the determination of accessible paths of chemical reactions computationally efficient.