Ion-Ion Correlation and Charge Reversal at Titrating Solid Interfaces

Christophe Labbez; Bo Jönsson; Michal Skarba; Michal Borkovec

doi:10.1021/la900853e

Ion-Ion Correlation and Charge Reversal at Titrating Solid Interfaces

Christophe Labbez, Bo Jönsson, Michal Skarba, Michal Borkovec

Computational Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Confronting grand canonical titration Monte Carlo simulations (MC) with recently published titration and charge reversal (CR) experiments on silica surfaces by Dove and Craven (Dove, P. M.; Craven, C. M. Geochim. Cosmochim. Acta 2005, 69, 4963-4970) and van der Heyden et al. (van der Heyden, F. H. J.; Stein, D.; Besteman, K.; Lemay, S. G.; Dekker, C. Phys. Rev. Lett. 2006, 96, 224502), we show that ion-ion correlations quantitatively explain why divalent counterions strongly promote surface charge which, in turn, eventually causes a CR. Titration and CR results from simulations and experiments are in excellent agreement without any fitting parameters. This is the first unambiguous evidence that ion-ion correlations arc instrumental in the creation of highly charged surfaces and responsible for their CR. Finally, we show that charge correlations result in "anomalous" charge regulation in strongly coupled conditions in qualitative disagreement with its classical treatment.

Original language	English
Pages (from-to)	7209-7213
Journal	Langmuir
Volume	25
Issue number	13
DOIs	https://doi.org/10.1021/la900853e
Publication status	Published - 2009

Bibliographical note

The information about affiliations in this record was updated in December 2015.
The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)

Subject classification (UKÄ)

Theoretical Chemistry

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10.1021/la900853e

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title = "Ion-Ion Correlation and Charge Reversal at Titrating Solid Interfaces",

abstract = "Confronting grand canonical titration Monte Carlo simulations (MC) with recently published titration and charge reversal (CR) experiments on silica surfaces by Dove and Craven (Dove, P. M.; Craven, C. M. Geochim. Cosmochim. Acta 2005, 69, 4963-4970) and van der Heyden et al. (van der Heyden, F. H. J.; Stein, D.; Besteman, K.; Lemay, S. G.; Dekker, C. Phys. Rev. Lett. 2006, 96, 224502), we show that ion-ion correlations quantitatively explain why divalent counterions strongly promote surface charge which, in turn, eventually causes a CR. Titration and CR results from simulations and experiments are in excellent agreement without any fitting parameters. This is the first unambiguous evidence that ion-ion correlations arc instrumental in the creation of highly charged surfaces and responsible for their CR. Finally, we show that charge correlations result in {"}anomalous{"} charge regulation in strongly coupled conditions in qualitative disagreement with its classical treatment.",

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note = "The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)",

year = "2009",

doi = "10.1021/la900853e",

language = "English",

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journal = "Langmuir",

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publisher = "The American Chemical Society (ACS)",

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T1 - Ion-Ion Correlation and Charge Reversal at Titrating Solid Interfaces

AU - Labbez, Christophe

AU - Jönsson, Bo

AU - Skarba, Michal

AU - Borkovec, Michal

N1 - The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)

PY - 2009

Y1 - 2009

N2 - Confronting grand canonical titration Monte Carlo simulations (MC) with recently published titration and charge reversal (CR) experiments on silica surfaces by Dove and Craven (Dove, P. M.; Craven, C. M. Geochim. Cosmochim. Acta 2005, 69, 4963-4970) and van der Heyden et al. (van der Heyden, F. H. J.; Stein, D.; Besteman, K.; Lemay, S. G.; Dekker, C. Phys. Rev. Lett. 2006, 96, 224502), we show that ion-ion correlations quantitatively explain why divalent counterions strongly promote surface charge which, in turn, eventually causes a CR. Titration and CR results from simulations and experiments are in excellent agreement without any fitting parameters. This is the first unambiguous evidence that ion-ion correlations arc instrumental in the creation of highly charged surfaces and responsible for their CR. Finally, we show that charge correlations result in "anomalous" charge regulation in strongly coupled conditions in qualitative disagreement with its classical treatment.

AB - Confronting grand canonical titration Monte Carlo simulations (MC) with recently published titration and charge reversal (CR) experiments on silica surfaces by Dove and Craven (Dove, P. M.; Craven, C. M. Geochim. Cosmochim. Acta 2005, 69, 4963-4970) and van der Heyden et al. (van der Heyden, F. H. J.; Stein, D.; Besteman, K.; Lemay, S. G.; Dekker, C. Phys. Rev. Lett. 2006, 96, 224502), we show that ion-ion correlations quantitatively explain why divalent counterions strongly promote surface charge which, in turn, eventually causes a CR. Titration and CR results from simulations and experiments are in excellent agreement without any fitting parameters. This is the first unambiguous evidence that ion-ion correlations arc instrumental in the creation of highly charged surfaces and responsible for their CR. Finally, we show that charge correlations result in "anomalous" charge regulation in strongly coupled conditions in qualitative disagreement with its classical treatment.

U2 - 10.1021/la900853e

DO - 10.1021/la900853e

M3 - Article

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SN - 0743-7463

VL - 25

SP - 7209

EP - 7213

JO - Langmuir

JF - Langmuir

IS - 13

ER -

Ion-Ion Correlation and Charge Reversal at Titrating Solid Interfaces

Abstract

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