Reactive conformations and non-Markovian reaction kinetics of a Rouse polymer searching for a target in confinement

TL;DR

This paper develops a detailed non-Markovian theoretical framework for reaction kinetics of a Rouse polymer in confinement, revealing significant deviations from Markovian predictions and providing new scaling laws and shape descriptions.

Contribution

It introduces a comprehensive non-Markovian theory for polymer reaction kinetics, surpassing previous models by capturing conformational dynamics and deriving scaling laws.

Findings

Non-Markovian effects are significant in 1D regimes.

Markovian models can overestimate reaction times by orders of magnitude.

Polymer shape at reaction exhibits a slow power-law spectrum.

Abstract

We investigate theoretically a diffusion-limited reaction between a reactant attached to a Rouse polymer and an external fixed reactive site in confinement. The present work completes and goes beyond a previous study [T. Gu\'erin, O. B\'enichou and R. Voituriez, Nat. Chem., 4, 268 (2012)] that showed that the distribution of the polymer conformations at the very instant of reaction plays a key role in the reaction kinetics, and that its determination enables the inclusion of non-Markovian effects in the theory. Here, we describe in detail this non-Markovian theory and we compare it with numerical stochastic simulations and with a Markovian approach, in which the reactive conformations are approximated by equilibrium ones. We establish the following new results. Our analysis reveals a strongly non-Markovian regime in 1D, where the Markovian and non-Markovian dependance of the relation time on the initial distance are different. In this regime, the reactive conformations are so different from equilibrium conformations that the Markovian expressions of the reaction time can be overestimated by several orders of magnitudes for long chains. We also show how to derive qualitative scaling laws for the reaction time in a systematic way that takes into account the different behaviors of monomer motion at all time and length scales. Finally, we also give an analytical description of the average elongated shape of the polymer at the instant of the reaction and we show that its spectrum behaves a a slow power-law for large wave numbers.