Persistent effects of inertia on diffusion-influenced reactions: Theoretical methods and applications.

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. Herein, we derive a modified Cattaneo-Vernotte model by applying the projection operator method to the Fokker-Planck-Kramers equation with a reaction sink. The same modified Cattaneo-Vernotte model can be derived by a Grad procedure. We show that the inertial effect influences the reaction rate coefficient differently depending on whether the intrinsic reaction rate constant in the reaction sink term depends on the solute relative velocity or not. The momentum relaxation effect can be expressed by a modified Smoluchowski equation including a memory kernel using the Cattaneo-Vernotte model. When the intrinsic reaction rate constant is independent of the reactant velocity and is localized, the modified Smoluchowski equation should be generalized to include a reaction term without a memory kernel. When the intrinsic reaction rate constant depends on the relative velocity of reactants, an additional reaction term with a memory kernel is required because of competition between the current density associated with the reaction and the diffusive flux during momentum relaxation. The competition effect influences even the long-time reaction rate coefficient.

Inertial dynamic effects on diffusion-influenced reactions: Approach based on the diffusive Cattaneo system.

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. We obtain explicit analytical expressions for the rates, which show that both bulk and geminate recombination rates are retarded appreciably at short times due to the inertial dynamics. In particular, we find a distinctive feature of the inertial dynamic effect on the survival probability of a geminate pair at short times, which can be manifested in experimental observations.

Accurate analytical calculation of the rate coefficient for the diffusion-controlled reactions due to hyperbolic diffusion.

Using an approach based on the diffusion analog of the Cattaneo-Vernotte differential model, we find the exact analytical solution to the corresponding time-dependent linear hyperbolic initial boundary value problem, describing irreversible diffusion-controlled reactions under Smoluchowski's boundary condition on a spherical sink. By means of this solution, we extend exact analytical calculations for the time-dependent classical Smoluchowski rate coefficient to the case that includes the so-called inertial effects, occurring in the host media with finite relaxation times. We also present a brief survey of Smoluchowski's theory and its various subsequent refinements, including works devoted to the description of the short-time behavior of Brownian particles. In this paper, we managed to show that a known Rice's formula, commonly recognized earlier as an exact reaction rate coefficient for the case of hyperbolic diffusion, turned out to be only its approximation being a uniform upper bound of the exact value. Here, the obtained formula seems to be of great significance for bridging a known gap between an analytically estimated rate coefficient on the one hand and molecular dynamics simulations together with experimentally observed results for the short times regime on the other hand. A particular emphasis has been placed on the rigorous mathematical treatment and important properties of the relevant initial boundary value problems in parabolic and hyperbolic diffusion theories.

Diffusion-influenced reaction rates for active "sphere-prolate spheroid" pairs and Janus dimers.

The purpose of this paper is twofold. First, we provide a concise introduction to the generalized method of separation of variables for solving diffusion problems in canonical domains beyond conventional arrays of spheres. Second, as an important example of its application in the theory of diffusion-influenced reactions, we present an exact solution of the axially symmetric problem on diffusive competition in an array of two active particles (including Janus dumbbells) constructed of a prolate spheroid and a sphere. In particular, we investigate how the reaction rate depends on sizes of active particles, spheroid aspect ratio, particles' surface reactivity, and distance between their centers.

Correction: Theory of diffusion-influenced reactions in complex geometries.

Correction for 'Theory of diffusion-influenced reactions in complex geometries' by Marta Galanti et al., Phys. Chem. Chem. Phys., 2016, DOI: .

Theory of diffusion-influenced reactions in complex geometries.

Chemical transformations involving the diffusion of reactants and subsequent chemical fixation steps are generally termed "diffusion-influenced reactions" (DIR). Virtually all biochemical processes in living media can be counted among them, together with those occurring in an ever-growing number of emerging nano-technologies. The role of the environment's geometry (obstacles, compartmentalization) and distributed reactivity (competitive reactants, traps) is key in modulating the rate constants of DIRs, and is therefore a prime design parameter. Yet, it is a formidable challenge to build a comprehensive theory that is able to describe the environment's "reactive geometry". Here we show that such a theory can be built by unfolding this many-body problem through addition theorems for special functions. Our method is powerful and general and allows one to study a given DIR reaction occurring in arbitrary "reactive landscapes", made of multiple spherical boundaries of given size and reactivity. Importantly, ready-to-use analytical formulas can be derived easily in most cases.

Diffusion-influenced reactions in a hollow nano-reactor with a circular hole.

Hollow nanostructures are paid increasing attention in many nanotechnology-related communities in view of their numerous applications in chemistry and biotechnology, e.g. as smart nanoreactors or drug-delivery systems. In this paper we consider irreversible, diffusion-influenced reactions occurring within a hollow spherical cavity endowed with a circular hole on its surface. Importantly, our model is not limited to small sizes of the aperture. In our scheme, reactants can freely diffuse inside and outside the cavity through the hole, and react at a spherical boundary of given size encapsulated in the chamber and endowed with a given intrinsic rate constant. We work out the solution of the above problem, enabling one to compute the reaction rate constant to any desired accuracy. Remarkably, we show that, in the case of narrow holes, the rate constant is extremely well-approximated by a simple formula that can be derived on the basis of simple physical arguments and that can be readily employed to analyze experimental data.

Asymptotic solution of the diffusion equation in slender impermeable tubes of revolution. I. The leading-term approximation.

The anisotropic 3D equation describing the pointlike particles diffusion in slender impermeable tubes of revolution with cross section smoothly depending on the longitudinal coordinate is the object of our study. We use singular perturbations approach to find the rigorous asymptotic expression for the local particles concentration as an expansion in the ratio of the characteristic transversal and longitudinal diffusion relaxation times. The corresponding leading-term approximation is a generalization of well-known Fick-Jacobs approximation. This result allowed us to delineate the conditions on temporal and spatial scales under which the Fick-Jacobs approximation is valid. A striking analogy between solution of our problem and the method of inner-outer expansions for low Knudsen numbers gas kinetic theory is established. With the aid of this analogy we clarify the physical and mathematical meaning of the obtained results.

Ligand binding in a spherical region randomly crowded by receptors.

This paper reports on some results concerning the binding of diffusing ligands in a spherical 3D region randomly filled by free receptors. It is shown that commonly accepted mean-field theory which is successfully used for bulk diffusion-controlled reactions cannot describe the behavior of ligand concentration in the diffusion layer close to the region boundary. To eliminate this drawback of the theory, we introduce a new complementary diffusion equation in the boundary layer with an appropriate matching condition. Using this equation, we find the characteristic ligand penetration length and total time-dependent flux of ligand binding to free receptors randomly distributed in a spherical region.

Exact solution for anisotropic diffusion-controlled reactions with partially reflecting conditions.

We investigate a generalization of the model of Solc and Stockmayer to describe the diffusion-controlled reactions between chemically anisotropic reactants taking into account the partially reflecting conditions on two parts of the reaction surface. The exact solution of the relevant mixed boundary-value problem was found for different ratios of the intrinsic rate constants. The results obtained may be used to test numerical programs that describe diffusion-controlled reactions in real systems of particles with anisotropic reactivity.