How much time does it take two molecules to react? If a reaction occurs upon contact, the answer to this question boils down to the classic first-passage time problem: find the random time it takes the two molecules to meet. However, this is not always the case as molecules switch stochastically between reactive and non-reactive states. In such cases, the reaction is said to be ``gated by the internal states of the molecules involved which could have a dramatic influence on kinetics. A unified, continuous-time, approach to gated reactions on networks was presented in [Phys. Rev. Lett. 127, 018301, 2021]. Here, we build on this recent advancement and develop an analogous discrete-time version of the theory. Similar to continuous-time, we employ a renewal approach to show that the gated reaction time can always be expressed in terms of the corresponding ungated first-passage and return times; which yields formulas for the generating function of the gated reaction-time distribution and its corresponding mean and variance. In cases where the mean reaction time diverges, we show that the long-time asymptotics of the gated problem is inherited from its ungated counterpart, where only the pre-factor of the power law tail changes. The discretization of time also gives rise to new phenomena that do not exist in the continuous-time analogue. Crucially, when the internal gating dynamics is in, or out of, phase with the spatial process governing molecular encounters resonance and anti-resonance phenomena emerge. These phenomena are illustrated using two case studies which also serve to show how the general approach presented herein greatly simplifies the analysis of gated reactions.
Download