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Establishing conditions for simulating hydrophobic solutes in electric fields by molecular dynamics

Effects of the long-range van der Waals treatment on the apparent particle mobility

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Abstract

Despite considerable effort over the last decade, the interactions between solutes and solvents in the presence of electric fields have not yet been fully understood. A very useful manner in which to study these systems is through the application of molecular dynamics (MD) simulations. However, a number of MD studies have shown a tremendous sensitivity of the migration rate of a hydrophobic solute to the treatment of the long range part of the van der Waals interactions. While the origin of this sensitivity was never explained, the mobility is currently regarded as an artifact of an improper simulation setup. We explain the spread in observed mobilites by performing extensive molecular dynamics simulations using the GROMACS software package on a system consisting of a model hydrophobic object (Lennard-Jones particle) immersed in water both in the presence and absence of a static electric field. We retrieve a unidirectional field-induced mobility of the hydrophobic object when the forces are simply truncated. Careful analysis of the data shows that, only in the specific case of truncated forces, a non-zero van der Waals force acts, on average, on the Lennard-Jones particle. Using the Stokes law we demonstrate that this force yields quantitative agreement with the field-induced mobility found within this setup. In contrast, when the treatment of forces is continuous, no net force is observed. In this manner, we provide a simple explanation for the previously controversial reports.

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Acknowledgments

We thank V. Knecht, K. Mecke und U. Felderhof for stimulating discussions. ASS and DMS acknowledge financial support from the Cluster of Excellence: Engineering of Advanced Materials, Erlangen, Germany. ZM acknowledges the partial financial support from BAYHOST.

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Authors and Affiliations

  1. Cluster of Excellence: Engineering of Advanced Materials, Friedrich-Alexander University Erlangen-Nuremberg, Nägelsbachstraße 49b, 91052, Erlangen, Germany

    Zoran Miličević, Ana-Sunčana Smith & David M. Smith

  2. Institute for Theoretical Physics, Friedrich-Alexander University Erlangen-Nuremberg, Staudtstraße 7, 91058, Erlangen, Germany

    Zoran Miličević & Ana-Sunčana Smith

  3. Ruđer Bošković Institute, Bijenička cesta 54, 10000, Zagreb, Croatia

    David M. Smith

  4. Groningen Biomolecular Sciences and Biotechnology Institute and Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 7, 9747AG, Groningen, The Netherlands

    Siewert J. Marrink

Authors
  1. Zoran Miličević
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  2. Siewert J. Marrink
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  3. Ana-Sunčana Smith
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  4. David M. Smith
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Corresponding authors

Correspondence to Ana-Sunčana Smith or David M. Smith.

Additional information

This paper belongs to a Topical Collection on the occasion of Prof. Tim Clark’s 65th birthday

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Miličević, Z., Marrink, S.J., Smith, AS. et al. Establishing conditions for simulating hydrophobic solutes in electric fields by molecular dynamics. J Mol Model 20, 2359 (2014). https://doi.org/10.1007/s00894-014-2359-5

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  • DOI: https://doi.org/10.1007/s00894-014-2359-5

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