In the first 650 reactive cycles, both approaches show similar trends in the number of candidates found (top row) and the selection probabilities (middle row), due to the use of kinetically corrected sampling. The resulting cascade of reactions and build-up of products (final row) is also similar. For the variable MD time, standard deviations in the species counts are smaller, particularly for cEC •-. The reaction cascade is less chaotic and more resilient to starting conditions due to the allocation of MD time. When the initial path selection probabilities are dominated by the barrierless path I, τ var calculated on-the-fly frequently falls below the τ min lower limit in Eqn. (5). These reductions are executed instantaneously in succession, with no MD being run between them.