Strong defocusing of molecular reaction times results from an interplay of geometry and reaction control - Archive ouverte HAL
Article Dans Une Revue Communications Chemistry Année : 2018

Strong defocusing of molecular reaction times results from an interplay of geometry and reaction control

Résumé

Textbook concepts of diffusion-versus kinetic-control are well-defined for reaction-kinetics involving macroscopic concentrations of diffusive reactants that are adequately described by rate-constants-the inverse of the mean-first-passage-time to the reaction-event. In contradistinction, an open important question is whether the mean-first-passage-time alone is a sufficient measure for biochemical reactions that involve nanomolar reactant concentrations. Here, using a simple yet generic, exactly-solvable model we study the conspiratory effect of diffusion and chemical reaction-limitations on the full reaction-time distribution. We show that it has a complex structure with four distinct regimes delimited by three characteristic time scales spanning a window of several decades. Consequently, the reaction-times are defocused: no unique timescale characterises the reaction-process, diffusion-and kinetic-control can no longer be disentangled, and it is imperative to know the full reaction-time distribution. We introduce the concepts of geometry-and reaction-control, and also quantify each regime by calculating the corresponding reaction depth.
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ArXiv 1911.00942 (2018) Grebenkov, Metzler, Oshanin [Strong defocusing of molecular reaction times results from an interplay of geometry and reaction control].pdf (635.61 Ko) Télécharger le fichier
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Dates et versions

hal-02346366 , version 1 (05-11-2019)

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Denis S Grebenkov, Ralf Metzler, Gleb Oshanin. Strong defocusing of molecular reaction times results from an interplay of geometry and reaction control. Communications Chemistry, 2018, 1, pp.96. ⟨10.1038/s42004-018-0096-x⟩. ⟨hal-02346366⟩
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