Nonequilibrium Spatial Correlations in Chemical Systems: Beyond Ornstein–zernike

Wakou, J.; Kitahara, Kakuo; Litniewski, Marek; Górecki, Jerzy

doi:10.1142/s0129183102004108

Cited by 3 publications

(3 citation statements)

References 11 publications

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“…Photo-electrochemical (PEC) conversion of water can be an example, but the fundamental results apply to other electrode reactions. We show that the gradient of total ion density (the sum of cation and anion concentrations) is characterized by either the Kuramoto length [26][27][28][29][30][31] Debye length depending on the situation, while the gradient of charge density (the difference between cation and anion concentrations) is characterized by the Debye length in binary monovalent weak electrolytes. The Kuramoto length characterizes the length scale of local density fluctuations around a uniform concentration state.…”

Section: Introductionmentioning

confidence: 96%

“…The Kuramoto length characterizes the length scale of local density fluctuations around a uniform concentration state. [26][27][28][29][30][31] In weak electrolytes, the Kuramoto length is given by the length scale of diffusive migration of ions within its life-time; the life-time is determined by the association rate of ions. [26][27][28][29][30][31] Our results indicate that the ion density gradients can also be characterized by the Kuramoto length when both cations and anions are discharged at the electrode in binary monovalent weak electrolytes.…”

Section: Introductionmentioning

confidence: 99%

“…[26][27][28][29][30][31] In weak electrolytes, the Kuramoto length is given by the length scale of diffusive migration of ions within its life-time; the life-time is determined by the association rate of ions. [26][27][28][29][30][31] Our results indicate that the ion density gradients can also be characterized by the Kuramoto length when both cations and anions are discharged at the electrode in binary monovalent weak electrolytes. For this case, ion density drop caused by electrode reactions is recovered by ion density fluctuations localized within the Kuramoto length.…”

Section: Introductionmentioning

confidence: 99%

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Possible influence of the Kuramoto length in a photo-catalytic water splitting reaction revealed by Poisson–Nernst–Planck equations involving ionization in a weak electrolyte

Suzuki

Seki

2018

Chemical Physics

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We studied ion concentration profiles and the charge density gradient caused by electrode reactions in weak electrolytes by using the Poisson-Nernst-Planck equations without assuming charge neutrality. In weak electrolytes, only a small fraction of molecules is ionized in bulk. Ion concentration profiles depend on not only ion transport but also the ionization of molecules. We considered the ionization of molecules and ion association in weak electrolytes and obtained analytical expressions for ion densities, electrostatic potential profiles, and ion currents. We found the case that the total ion density gradient was given by the Kuramoto length which characterized the distance over which an ion diffuses before association. The charge density gradient is characterized by the Debye length for 1:1 weak electrolytes. We discuss the role of these length scales for efficient water splitting reactions using photo-electrocatalytic electrodes.

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Section: Introductionmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Possible influence of the Kuramoto length in a photo-catalytic water splitting reaction revealed by Poisson–Nernst–Planck equations involving ionization in a weak electrolyte

Suzuki

Seki

2018

Chemical Physics

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The influence of the quencher concentration on the rate of simple bimolecular reaction: Molecular dynamics study

Litniewski

2005

The Journal of Chemical Physics

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The paper presents the results of large-scale molecular dynamics simulations of the irreversible bimolecular reaction A+B --> C+B for the simple liquid composed of mechanically identical soft spheres. The systems with the total number of molecules corresponding to 10(7)-10(9) are considered. The influence of the concentration of a quencher (B) on the surviving probability of A and the reaction rate is analyzed for a wide range of the concentrations and for two significantly different reduced densities. It is shown that the quencher concentration dependence effect (QCDE) is, in fact, a composition of two QCDE effects: the short-time QCDE that increases the reaction rate and the long-time QCDE that decreases it. The paper also analyzes the influence of the concentration on the steady-state rate constant, k(ss), obtained by integrating the surviving probability. The excess in k(ss) due to finite quencher concentration changes the sign from negative to positive while going from low to high concentrations. Generally, the excess is extremely weak. It attains a 1% level only if the concentration is very high.

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The influence of the quencher concentration on the rate of simple bimolecular reaction: Molecular dynamics study. II

Litniewski

2006

The Journal of Chemical Physics

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In this paper new results of the simulations [M. Litniewski, J. Chem. Phys. 123, 124506 (2005)] on the influence of the quencher concentration on the reaction A+B-->C+B for the identical soft sphere system are presented. The problem is generalized by considering also the case when the spheres are immersed in the Brownian medium. A significant difference between simple deterministic systems and the Brownian ones is found: the excess in the rate coefficient for the Brownian system is constant and positive, except for very short times. The reaction has been simulated for a very long time, but any tendency to decrease the excess has not been noted. It is also shown that the relative excess in the surviving probability is a universal quadratic function of the quencher concentration for the range of time much longer than the result from the previous simulations. A very strong correlation between the excess in the relative value of spatial correlations between the reagents and the excess in the rate coefficient is shown. It is also shown that the A-A and A-C interactions have some influence on the excess values. A simple model for this effect is presented.

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Nonequilibrium Spatial Correlations in Chemical Systems: Beyond Ornstein–zernike

Cited by 3 publications

References 11 publications

Possible influence of the Kuramoto length in a photo-catalytic water splitting reaction revealed by Poisson–Nernst–Planck equations involving ionization in a weak electrolyte

Possible influence of the Kuramoto length in a photo-catalytic water splitting reaction revealed by Poisson–Nernst–Planck equations involving ionization in a weak electrolyte

The influence of the quencher concentration on the rate of simple bimolecular reaction: Molecular dynamics study

The influence of the quencher concentration on the rate of simple bimolecular reaction: Molecular dynamics study. II

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