Theoretical calculations of the unimolecular canonical rate constants

Microcanonical rate constants k(E) and canonical rate constants k(T) for unimolecular reactions have been obtained through the calculations of cumulative reaction probabilities N(E) with the unsymmetrical Eckart potential tunneling correction. By way of example, the reactions HCN → CNH (I) and FNC → NCF (II) have been employed. For reaction (I), the calculated rate constants are in agreement with the experimental data; for reaction (II), the results are in accordance with the rate constants k^CVT/MEPSAG(T) calculated by the common program POLYRATE.