Energy Decomposition along Reaction Coordinate: Theory and Applications to Nonequilibrium Ensembles of Trajectories.

A theoretical framework is proposed for an energy decomposition scheme along the reaction coordinate, in which the ensemble average of the potential energy weighted with reactive flux intensity is decomposed into energy components at the per-coordinate level. The decomposed energy quantity is demonstrated to be closely related to the free energy along the reaction coordinate, and its connection to the emergent potential energy is provided. In the application to alanine dipeptide under vacuum, illustrative calculations were performed in three nonequilibrium ensembles of trajectories: (1) transition path ensemble sampled with transition path sampling; (2) ensemble of short trajectories initiated from configurations around the transition-state region; and (3) ensemble of short trajectories shooting from configurations in several transition paths. The energy components on each coordinate were found to be consistent among the three ensembles of trajectories, indicating a broad applicability of the approach in biomolecular studies. In addition, the free energies along an optimized reaction coordinate obtained with these nonequilibrium ensembles were largely overlapped with a reference free energy calculated from a long equilibrium trajectory.