A refined ring polymer molecular dynamics theory of chemical reaction rates

We further develop the ring polymer molecular dynamics (RPMD) method for calculating chemical reaction rates [I. R. Craig and D. E. Manolopoulos, J. Chem. Phys. 122, 084106 (2005)]. We begin by showing how the rate coefficient we obtained before can be calculated in a more efficient way by considering the side functions of the ring-polymer centroids, rather than averaging over the side functions of the individual ring-polymer beads. This has two distinct advantages. First, the statistics of the phase-space average over the ring-polymer coordinates and momenta are greatly improved. Second, the resulting flux-side correlation function converges to its long-time limit much more rapidly. Indeed the short-time limit of this flux-side correlation function already provides a "quantum transition state theory" approximation to the final rate coefficient. In cases where transition state recrossing effects are negligible, and the transition state dividing surface is put in the right place, the RPMD rate is therefore obtained almost instantly. We then go on to show that the long-time limit of the new flux-side correlation function, and hence the fully converged RPMD reaction rate, is rigorously independent of the choice of the transition state dividing surface. This is especially significant because the optimum dividing surface can often be very difficult to determine for reactions in complex chemical systems. (c) 2005 American Institute of Physics.