A multiple decay-length extension of the Debye–Hückel theory: to achieve high accuracy also for concentrated solutions and explain under-screening in dilute symmetric electrolytes

Kjellander, Roland

doi:10.1039/d0cp02742a

Cited by 48 publications

(60 citation statements)

References 106 publications

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“…Here, we outline an argument why this is expected for a linear theory. Such an equivalence has recently been observed by Kjellander with regard to his Multiple-Decay Extended Debye-Hückel MDE-DH theory of electrolytes [44].…”

Section: Equivalence Of Lnγsupporting

confidence: 59%

“…Similarly, in the analysis of numerically intensive theoretical problems (see for example, reference [52]) the use of LMPB analytical expressions as initial input in iterative processes can prove to be useful. Furthermore, the success of the LMPB approach in analyzing the thermodynamics of 1:1 valency systems makes this a potentially attractive method that can be used to explore more complex situations such as higher valency systems [44] and/or systems with a variable dielectric constant [53]. Studies of higher valency and mixed electrolyte systems would also be useful in order to see the limitations of the LMPB theories.…”

Section: Discussionmentioning

confidence: 99%

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Structure and thermodynamics in the linear modified Poisson-Boltzmann theories in restricted primitive model electrolytes

Bhuiyan¹

2021

Condens. Matter Phys.

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Structure and thermodynamics in restricted primitive model electrolytes are examined using three recently developed versions of a linear form of the modified Poisson-Boltzmann equation. Analytical expressions for the osmotic coefficient and the electrical part of the mean activity coefficient are obtained and the results for the osmotic and the mean activity coefficients are compared with that from the more established mean spherical approximation, symmetric Poisson-Boltzmann, modified Poisson-Boltzmann theories, and available Monte Carlo simulation results. The linear theories predict the thermodynamics to a remarkable degree of accuracy relative to the simulations and are consistent with the mean spherical approximation and modified Poisson-Boltzmann results. The predicted structure in the form of the radial distribution functions and the mean electrostatic potential also compare well with the corresponding results from the formal theories. The excess internal energy and the electrical part of the mean activity coefficient are shown to be identical analytically for the mean spherical approximation and the linear modified Poisson-Boltzmann theories.

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Section: Equivalence Of Lnγsupporting

confidence: 59%

Section: Discussionmentioning

confidence: 99%

Structure and thermodynamics in the linear modified Poisson-Boltzmann theories in restricted primitive model electrolytes

Bhuiyan¹

2021

Condens. Matter Phys.

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“…Atomistic and coarse grained simulations have observed a screening length that seems to agree with the short-range 'structural force' observed in experiments, but not the long decay length [14]. Many theoretical approaches attempt to explain the data by introducing the idea of ion pairs [9,10] or effective dielectric constants [15]. The argument is that most cations and anions are bundled up as neutral pairs in concentrated electrolytes, thus the electrolyte comprises a low concentration of 'free' ions solvated in a liquid of effectively neutral 'paired' ions.…”

mentioning

confidence: 99%

Bayesian unsupervised learning reveals hidden structure in concentrated electrolytes

Jones,

Coupette,

Härtel

et al. 2020

Preprint

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Electrolytes play an important role in a plethora of applications ranging from energy storage to biomaterials. Notwithstanding this, the structure of concentrated electrolytes remains enigmatic.Many theoretical approaches attempt to model the concentrated electrolytes by introducing the idea of ion pairs, with ions either being tightly 'paired' with a counter-ion, or 'free' to screen charge. In this study we reframe the problem into the language of computational statistics, and test the null hypothesis that all ions share the same local environment. Applying the framework to molecular dynamics simulations, we show that this null hypothesis is not supported by data. Our statistical technique suggests the presence of distinct local ionic environments; surprisingly, these differences arise in like charge correlations rather than unlike charge attraction. The resulting fraction of particles in non-aggregated environments shows a universal scaling behaviour across different background dielectric constants and ionic concentrations.

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“…[60]. A very recent paper [98] introduced some new modifications/extensions of DH theory which make predictions for decay lengths. As far as we can tell, these are not significantly different from the results we present here.…”

Section: Summary and Discussionmentioning

confidence: 99%

“…Another obvious candidate is the omission of polarizability; this is absent completely in the RPM and is, at best, included approximately in some of the explicit-solvent models. An interesting approach was put forward by Kjellander [98,102,103], who shows that electrostatic screening and the static dielectric function ε(k), with wave-number k, are intimately coupled, such that the long-wavelength limit ε(0) equals the static dielectric constant only in the absence of ions, e.g in dipolar fluids or non-electrolytes, but not in their presence.…”

Section: Discussionmentioning

confidence: 99%

The Electrode-Electrolyte Interface from the perspective of Density Functional Theory

Cats¹

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Odin, the chief of the Aesir (Norse gods), has many names and is often portrayed as an old man, dressed in grey, with a wide-brimmed hat, and one eye. Odin is constantly in pursuit of gaining knowledge and wisdom, often in exchange of a sacrifice; he gave his eye to drink from the well of Mimir, which contains much wisdom, and even hung himself at Yggdrasil (the world tree) pierced by his own spear Gungnir for nine days and nights in order to understand the runes, which also contained wisdom and knowledge. He does not seek knowledge and wisdom only for himself, but he wants to learn anything that might prevent catastrophe at Ragnarok. Moreover in the poem Hávamál (part of the Edda), meaning "words of the high one" (a reference to Odin), he gives wisdom and advice on how to live a good life, e.g. never stop learning, and do not drink too much alcohol.

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A multiple decay-length extension of the Debye–Hückel theory: to achieve high accuracy also for concentrated solutions and explain under-screening in dilute symmetric electrolytes

Abstract: The Poisson-Boltzmann and Debye-Hückel approximations for the pair distributions and mean electrostatic potential in electrolytes predict that these entities have one single decay mode with a decay length equal to...

Cited by 48 publications

References 106 publications

Structure and thermodynamics in the linear modified Poisson-Boltzmann theories in restricted primitive model electrolytes

Structure and thermodynamics in the linear modified Poisson-Boltzmann theories in restricted primitive model electrolytes

Bayesian unsupervised learning reveals hidden structure in concentrated electrolytes

The Electrode-Electrolyte Interface from the perspective of Density Functional Theory

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