Efficient Procedure to Compute the Microcanonical Volume of Initial Conditions that Lead to Escape Trajectories from a Multidimensional Potential Well

A procedure is presented for computing the phase space volume of initial conditions for trajectories that escape or “react” from a multidimensional potential well. The procedure combines a phase space transition state theory, which allows one to construct dividing surfaces that are free of local recrossing and that minimize the directional flux, and a classical spectral theorem. The procedure gives the volume of reactive initial conditions in terms of a sum over each entrance channel of the well of the product of the phase space flux across the dividing surface associated with the channel and the mean residence time in the well of trajectories which enter through the channel. This approach is illustrated for HCN isomerization in three dimensions, for which the method is several orders of magnitude more efficient than standard Monte Carlo sampling.