Simple closed-form expressions are presented for the time-dependent rate coefficients of diffusion-influenced reactions in the presence of spherically symmetric potentials. For diffusion-controlled contact reactions, our expression reproduces the first two terms in both the short- and long-time expansions of the rate coefficient. At intermediate times, agreement with numerical results for the Debye-Hückel potential is found to be within a few percent for a wide range of parameters. For diffusion-influenced contact reactions (described by the radiation boundary condition), the agreement is even better. When the reactivity depends on the distance between the reactants (e.g., exponentially), our analytic result is less accurate, because it reproduces the two terms in the long-time expansion only to the linear order of the reciprocal of the diffusion coefficient. Our results should prove useful in the analysis of experimental data for diffusion-influenced reactions with centrosymmetric interaction potentials.
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http://dx.doi.org/10.1021/jp044433q | DOI Listing |
J Chem Phys
August 2024
Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, 4 Kosygina St., 119991 Moscow, Russian Federation.
Motivated by the various applications of the trapping diffusion-influenced reaction theory in physics, chemistry, and biology, this paper deals with irreducible Cartesian tensor (ICT) technique within the scope of the generalized method of separation of variables (GMSV). We provide a survey from the basic concepts of the theory and highlight the distinctive features of our approach in contrast to similar techniques documented in the literature. The solution to the stationary diffusion equation under appropriate boundary conditions is represented as a series in terms of ICT.
View Article and Find Full Text PDFJ Chem Phys
October 2023
National Institute of Advanced Industrial Science and Technology (AIST), Higashi 1-1-1 AIST Central 5, Tsukuba, Ibaraki, Japan.
The Cattaneo-Vernotte model has been widely studied to take momentum relaxation into account in transport equations. Yet, the effect of reactions on the Cattaneo-Vernotte model has not been fully elucidated. At present, it is unclear how the current density associated with reactions can be expressed in the Cattaneo-Vernotte model.
View Article and Find Full Text PDFJ Chem Phys
October 2023
Division of Chemical Engineering, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.
The returning probability (RP) theory, a rigorous diffusion-influenced reaction theory, enables us to analyze the binding process systematically in terms of thermodynamics and kinetics using molecular dynamics (MD) simulations. Recently, the theory was extended to atomistically describe binding processes by adopting the host-guest interaction energy as the reaction coordinate. The binding rate constants can be estimated by computing the thermodynamic and kinetic properties of the reactive state existing in the binding processes.
View Article and Find Full Text PDFJ Chem Phys
May 2023
Department of Chemistry, Seoul National University, Seoul 08826, South Korea and N.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, 4 Kosygina St., 119991 Moscow, Russian Federation.
We investigate the inertial dynamic effects on the kinetics of diffusion-influenced reactions by solving the linear diffusive Cattaneo system with the reaction sink term. Previous analytical studies on the inertial dynamic effects were limited to the bulk recombination reaction with infinite intrinsic reactivity. In the present work, we investigate the combined effects of inertial dynamics and finite reactivity on both bulk and geminate recombination rates.
View Article and Find Full Text PDFInt J Mol Sci
April 2023
International Tomography Center SB RAS, 630090 Novosibirsk, Russia.
The influence of magnetic fields on chemical reactions, including biological ones, has been and still is a topical subject in the field of scientific research. Experimentally discovered and theoretically substantiated magnetic and spin effects in chemical radical reactions form the basis of research in the field of spin chemistry. In the present work, the effect of a magnetic field on the rate constant of the bimolecular spin-selective recombination of radicals in the bulk of a solution is considered theoretically for the first time, taking into account the hyperfine interaction of radical spins with their magnetic nuclei.
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