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A test of improved force field parameters for urea: molecular-dynamics simulations of urea crystals

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Abstract

Molecular-dynamics (MD) simulations of urea crystals of different shapes (cubic, rectangular prismatic, and sheet) have been performed using our previously published force field for urea. This force field has been validated by calculating values for the cohesive energy, sublimation temperature, and melting point from the MD data. The cohesive energies computed from simulations of cubic and rectangular prismatic urea crystals in vacuo at 300 K agreed very well with the experimental sublimation enthalpies reported at 298 K. We also found very good agreement between the melting points as observed experimentally and from simulations. Annealing the crystals just below the melting point leads to reconstruction to form crystal faces that are consistent with experimental observations. The simulations reveal a melting mechanism that involves surface (corner/edge) melting well below the melting point, and rotational disordering of the urea molecules in the corner/edge regions of the crystal, which then facilitates the translational motion of these molecules.

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Acknowledgments

This work was supported by the Deutsche Forschungsgemeinschaft as part of the project PE 42710-2 and the Excellence Cluster Engineering of Advanced Materials.

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Authors and Affiliations

  1. Department of Chemistry, Natural Sciences, Architecture and Engineering Faculty, Bursa Technical University, Osmangazi, 16000, Bursa, Turkey

    Gül Altınbaş Özpınar

  2. Computer-Chemie-Centrum and Interdisciplinary Center for Molecular Materials, Friedrich-Alexander Universität Erlangen-Nürnberg, Nägelsbachstr. 25, 91052, Erlangen, Germany

    Gül Altınbaş Özpınar, Frank R. Beierlein, Dirk Zahn & Timothy Clark

  3. Excellence Cluster Engineering of Advanced Materials, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstr. 49b, 91052, Erlangen, Germany

    Gül Altınbaş Özpınar, Frank R. Beierlein, Wolfgang Peukert, Dirk Zahn & Timothy Clark

  4. Lehrstuhl für Feststoff- und Grenzflächenverfahrenstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Cauerstraße 4, 91058, Erlangen, Germany

    Wolfgang Peukert

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  1. Gül Altınbaş Özpınar
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  2. Frank R. Beierlein
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Correspondence to Timothy Clark.

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Gül Altınbaş Özpınar and Frank R. Beierlein contributed equally to this work

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Özpınar, G.A., Beierlein, F.R., Peukert, W. et al. A test of improved force field parameters for urea: molecular-dynamics simulations of urea crystals. J Mol Model 18, 3455–3466 (2012). https://doi.org/10.1007/s00894-011-1336-5

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