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Recent work has shown that in a non-thermal, multidimensional system, thetrajectories in the activated complex possess different instantaneous andtime-averaged reactant decay rates. Under dissipative dynamics, it is knownthat these trajectories, which are bound on the normally hyperbolic invariantmanifold (NHIM), converge to a single trajectory over time. By subjecting thesedissipative systems to thermal noise, we find fluctuations in the saddle-boundtrajectories and their instantaneous decay rates. Averaging over theseinstantaneous rates results in the decay rate of the activated complex in athermal system. We find, that the temperature dependence of the activatedcomplex decay in a thermal system can be linked to the distribution of thephase space resolved decay rates on the NHIM in the non-dissipative case. Byadjusting the external driving of the reaction, we show that it is possible toinfluence how the decay rate of the activated complex changes with risingtemperature.

Thermal decay rates of an activated complex in a driven model chemical reaction