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Foundations of Molecular Modeling and Simulation pp 107–123Cite as

Homogeneous Nucleation of [dmim+][Cl−] from its Supercooled Liquid Phase: A Molecular Simulation Study

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Abstract

We have used molecular simulations to study the homogeneous nucleation of the ionic liquid [dmim+][Cl−] from its bulk supercooled liquid at 340 K. Our combination of methods include the string method in collective variables (Maragliano et al., J. Chem. Phys. 125:024106, 2006), Markovian milestoning with Voronoi tessellations (Maragliano et al J Chem Theory Comput 5:2589, 2009), and order parameters for molecular crystals (Santiso and Trout J Chem Phys 134:064109, 2011). The minimum free energy path, the approximate size of the critical nucleus, the free energy barrier and the rates involved in the homogeneous nucleation process were determined from our simulations. Our results suggest that the subcooled liquid (58 K of supercooling) has to overcome a free energy barrier of ~85 kcal/mol, and has to form a critical nucleus of size ~3.4 nm; this nucleus then grows to form the monoclinic crystal phase. A nucleation rate of 6.6 × 1010 cm−3 s−1 was determined from our calculations, which agrees with values observed in experiments and simulations of homogeneous nucleation of subcooled water.

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Acknowledgments

We are grateful to Isiah Warner and his group (Chemistry, LSU) for helpful discussions. This work was partially supported by the National Science Foundation (CAREER Award CBET-1253075, and EPSCoR Cooperative Agreement EPS-1003897), and by the Louisiana Board of Regents. High-performance computational resources for this research were provided by High Performance Computing at Louisiana State University (http://www.hpc.lsu.edu) and by the Louisiana Optical Network Initiative (http://www.loni.org).

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Authors and Affiliations

  1. Cain Department of Chemical Engineering, Louisiana State University, Baton Rouge, LA, 70803, USA

    Xiaoxia He, Yan Shen & Francisco R. Hung

  2. Center for Computation & Technology, Louisiana State University, Baton Rouge, LA, 70803, USA

    Francisco R. Hung

  3. Department of Chemical and Biomolecular Engineering, North Carolina State University, Raleigh, NC, 27695, USA

    Erik E. Santiso

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  1. Department of Chemical &, Northwestern University, Evanston, Illinois, USA

    Randall Q Snurr

  2. Chemical Engineering, Imperial College London, London, United Kingdom

    Claire S. Adjiman

  3. York Buffalo, The State University of New, Buffalo, New York, USA

    David A. Kofke

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He, X., Shen, Y., Hung, F.R., Santiso, E.E. (2016). Homogeneous Nucleation of [dmim+][Cl−] from its Supercooled Liquid Phase: A Molecular Simulation Study. In: Snurr, R., Adjiman, C., Kofke, D. (eds) Foundations of Molecular Modeling and Simulation. Molecular Modeling and Simulation. Springer, Singapore. https://doi.org/10.1007/978-981-10-1128-3_7

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