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Charge fluctuations in charge-regulated systems: dependence on statistical ensemble

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Abstract

We investigate charge regulation of nanoparticles in concentrated suspensions, focusing on the effect of different statistical ensembles. We find that the choice of ensemble does not affect the mean charge of nanoparticles, but significantly alters the magnitude of its fluctuation. Specifically, we compared the behaviors of colloidal charge fluctuations in the semi-grand canonical and canonical ensembles and identified significant differences between the two. The choice of ensemble—whether the system is isolated or is in contact with a reservoir of acid and salt—will, therefore, affect the Kirkwood–Shumaker fluctuation-induced force inside concentrated suspensions. Our results emphasize the importance of selecting an appropriate ensemble that accurately reflects the experimental conditions when studying fluctuation-induced forces between polyelectrolytes, proteins, and colloidal particles in concentrated suspensions.

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All data generated or analyzed during the reported research are presented in the article.

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Acknowledgements

This work was partially supported by the CNPq, the CAPES, and the National Institute of Science and Technology Complex Fluids INCT-FCx.

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  1. Instituto de Física, Universidade Federal do Rio Grande do Sul, Porto Alegre, RS, 91501-970, Brazil

    Amin Bakhshandeh & Yan Levin

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  1. Amin Bakhshandeh
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YL developed theory. AB performed simulations. Both authors wrote the paper.

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Correspondence to Yan Levin.

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Bakhshandeh, A., Levin, Y. Charge fluctuations in charge-regulated systems: dependence on statistical ensemble. Eur. Phys. J. E 46, 65 (2023). https://doi.org/10.1140/epje/s10189-023-00325-3

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