A time correlation correlating signed initial flux through a dividing surface with product-side occupation at a later time. Dividing by reactant population gives a rate on a plateau after microscopic recrossing and before macroscopic equilibration.
Put the dividing surface at . The immediate positive flux includes all positive momenta and gives , an overestimate. Trajectories with hit the barrier, return across this surface, and cease contributing to the later product-side indicator. After their recrossing transient, only survives:
The exact rate is again unchanged; the transmission correction to the reactant-side transition-state estimate is . The return time depends on surface placement and velocity, so the plateau means a timescale-separated limiting flux, not the claim that every trajectory has one identical finite recrossing time.
Choose a reaction coordinate that is negative in the reactant region and positive in the product region; defines a dividing surface. With unnormalized canonical phase-space averaging, define
The signed initial flux counts both directions, while the later side function tests product commitment. The rate is on a plateau after microscopic recrossings have died away but before reactant depletion and global equilibration become important. The limit instead gives the transition-state-theory positive flux and can overcount trajectories that later return. A suitable dividing surface changes that early flux but not a correctly evaluated committed plateau rate. This correlation formulation provides the dynamical correction to a transition-state estimate.[ref]