Universal kinetics of imperfect reactions in confinement
VOITURIEZ, Raphaël
Laboratoire de Physique Théorique de la Matière Condensée [LPTMC]
Laboratoire Jean Perrin [LJP]
< Leer menos
Laboratoire de Physique Théorique de la Matière Condensée [LPTMC]
Laboratoire Jean Perrin [LJP]
Idioma
en
Article de revue
Este ítem está publicado en
Communications Chemistry. 2021-11-11, vol. 4, n° 1
Nature Research
Resumen en inglés
Chemical reactions generically require that particles come into contact. In practice, reaction is often imperfect and can necessitate multiple random encounters between reactants. In confined geometries, despite notable ...Leer más >
Chemical reactions generically require that particles come into contact. In practice, reaction is often imperfect and can necessitate multiple random encounters between reactants. In confined geometries, despite notable recent advances, there is to date no general analytical treatment of such imperfect transport-limited reaction kinetics. Here, we determine the kinetics of imperfect reactions in confining domains for any diffusive or anomalously diffusive Markovian transport process, and for different models of imperfect reactivity. We show that the full distribution of reaction times is obtained in the large confining volume limit from the knowledge of the mean reaction time only, which we determine explicitly. This distribution for imperfect reactions is found to be identical to that of perfect reactions upon an appropriate rescaling of parameters, which highlights the robustness of our results. Strikingly, this holds true even in the regime of low reactivity where the mean reaction time is independent of the transport process, and can lead to large fluctuations of the reaction time-even in simple reaction schemes. We illustrate our results for normal diffusion in domains of generic shape, and for anomalous diffusion in complex environments, where our predictions are confirmed by numerical simulations.< Leer menos
Palabras clave en inglés
Chemical physics
Reaction kinetics and dynamics
Reaction mechanisms
Structural properties
Orígen
Importado de HalCentros de investigación