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On the time dependence of rate coefficients of irreversible reactions between reactants with anisotropic reactivity in liquid solutions.
- Source :
-
Journal of Chemical Physics . 2016, Vol. 145 Issue 6, p1-11. 11p. 2 Diagrams, 5 Graphs. - Publication Year :
- 2016
-
Abstract
- Time dependence of the rate coefficients of sterically specific reactions is analyzed theoretically. Generally, such reactions exhibit a non-trivial dependence of their rate constant on the steric factor, < 1, which is defined as the fraction of reactive surface area. Notably, the rate constant of a diffusion-controlled reaction is proportional not to but, counter-intuitively, to√ due to partial averaging of the reaction anisotropy by translational diffusion. Here we demonstrate that the effective steric factor of a diffusion-influenced reaction is strongly time-dependent, increasing from f to √. When reactants have several active sites, these sites "interfere" each other in the sense that the rate constant depends on their relative positions. We demonstrate that such an interference effect is strongly time-dependent as well: it is absent at t = 0 but builds up with time. We argue that the outlined effects are also of importance for calculating the fluorescence quenching rate constants. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00219606
- Volume :
- 145
- Issue :
- 6
- Database :
- Academic Search Index
- Journal :
- Journal of Chemical Physics
- Publication Type :
- Academic Journal
- Accession number :
- 117540356
- Full Text :
- https://doi.org/10.1063/1.4960174