The long-time behavior of reversible binary reactions: Theory, Brownian simulations and experiment

Noam Agmon*, Arieh L. Edelstein

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

32 Scopus citations

Abstract

Many-body effects on reversible pseudo-unimolecular reactions are investigated using a combination of theory, simulation, and experiment. Theoretically, we rederive the superposition approximation starting from the fundamental N-particle equations. All the relations obtained are actually rigorous, except for a requirement that the concentration profile outside a vacant trap obeys a diffusion equation. Our derivation also yields a new numerical procedure for evaluating the superposition solution. Brownian dynamics simulations of one-dimensional competitive binding are presented over an unprecedented time regime. Comparison with the superposition approximation shows that this mean-field theory is exact at infinite dilution, but breaks down at high particle concentration. The main discrepancy is not at asymptotically long times as previously suspected, but rather at intermediate times, where a new power law-phase emerges. This is reflected in a maximum in the logarithmic derivative of the survival probability, which is more pronounced in our simulation as compared with the approximate theory. Finally, we show that the transient fluorescence data from an excited dye molecule which transfers a proton reversibly to water, develops a similar maximum in its logarithmic derivative at low pH values.

Original languageEnglish
Pages (from-to)4181-4187
Number of pages7
JournalThe Journal of Chemical Physics
Volume100
Issue number6
DOIs
StatePublished - 1994

Fingerprint

Dive into the research topics of 'The long-time behavior of reversible binary reactions: Theory, Brownian simulations and experiment'. Together they form a unique fingerprint.

Cite this