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.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Tesfai, A., El-Zahab, B., Bwambok, D.K., Baker, G.A., Fakayode, S.O., Lowry, M., Warner, I.M.: Controllable formation of ionic liquid micro- and nanoparticles via a melt-emulsion-quench approach. Nano Lett. 8, 897–901 (2008)
Tesfai, A., El-Zahab, B., Kelley, A.T., Li, M., Garno, J.C., Baker, G.A., Warner, I.M.: Magnetic and nonmagnetic nanoparticles from a group of uniform materials based on organic salts. ACS Nano 3, 3244–3250 (2009)
Bwambok, D.K., El-Zahab, B., Challa, S.K., Li, M., Chandler, L., Baker, G.A., Warner, I.M.: Near-Infrared fluorescent NanoGUMBOS for biomedical imaging. ACS Nano 3, 3854–3860 (2009)
Das, S., Bwambok, D., El-Zahab, B., Monk, J., de Rooy, S.L., Challa, S., Li, M., Hung, F.R., Baker, G.A., Warner, I.M.: Nontemplated approach to tuning the spectral properties of cyanine-based fluorescent nanogumbos. Langmuir 26, 12867–12876 (2010)
Dumke, J.C., El-Zahab, B., Challa, S., Das, S., Chandler, L., Tolocka, M., Hayes, D.J., Warner, I.M.: Lanthanide-based luminescent NanoGUMBOS. Langmuir 26, 15599–15603 (2010)
de Rooy, S.L., El-Zahab, B., Li, M., Das, S., Broering, E., Chandler, L., Warner, I.M.: Fluorescent one-dimensional nanostructures from a group of uniform materials based on organic salts. Chem. Commun. 47, 8916–8918 (2011)
Warner, I.M., El-Zahab, B., Siraj, N.: Perspectives on moving ionic liquid chemistry into the solid phase. Anal. Chem. 86, 7184–7191 (2014)
Thomas, W.P.W.: Ionic Liquids in Synthesis. Wilet-VCH, Weinheim (2008)
Plechkova, N.V., Seddon, K.R.: Applications of ionic liquids in the chemical industry. Chem. Soc. Rev. 37, 123–150 (2008)
Le Bideau, J., Viau, L., Vioux, A.: Ionogels, ionic liquid based hybrid materials. Chem. Soc. Rev. 40, 907–925 (2011)
Sha, M., Wu, G., Fang, H., Zhu, G., Liu, Y.: Liquid-to-solid phase transition of a 1,3-dimethylimidazolium chloride ionic liquid monolayer confined between graphite walls. J. Phys. Chem. C 112, 18584–18587 (2008)
Sha, M., Wu, G., Liu, Y., Tang, Z., Fang, H.: Drastic phase transition in ionic liquid Dmim CI confined between graphite walls: new phase formation. J. Phys. Chem. C 113, 4618–4622 (2009)
Pinilla, C., Del Popolo, M.G., Kohanoff, J., Lynden-Bell, R.M.: Polarization relaxation in an ionic liquid confined between electrified walls. J. Phys. Chem. B 111, 4877–4884 (2007)
Pinilla, C., Del Popolo, M.G., Lynden-Bell, R.M., Kohanoff, J.: Structure and dynamics of a confined ionic liquid. topics of relevance to dye-sensitized solar cells. J. Phys. Chem. B 109, 17922–17927 (2005)
Youngs, T.G.A., Hardacre, C.: Application of static charge transfer within an ionic-liquid force field and its effect on structure and dynamics. ChemPhysChem 9, 1548–1558 (2008)
Hanke, C.G., Atamas, N.A., Lynden-Bell, R.M.: Solvation of small molecules in imidazolium ionic liquids: a simulation study. Green Chem. 4, 107–111 (2002)
Del Popolo, M.G., Lynden-Bell, R.M., Kohanoff, J.: Ab initio molecular dynamics simulation of a room temperature ionic liquid. J. Phys. Chem. B 109, 5895–5902 (2005)
Buhl, M., Chaumont, A., Schurhammer, R., Wipff, G.: Ab initio molecular dynamics of liquid 1,3-dimethylimidazolium chloride. J. Phys. Chem. B 109, 18591–18599 (2005)
Monk, J., Singh, R., Hung, F.R.: Effects of Pore size and pore loading on the properties of ionic liquids confined inside nanoporous CMK-3 carbon materials. J. Phys. Chem. C 115, 3034–3042 (2011)
Debenedetti, P.G.: Metastable Liquids: Concepts and Principles. Princeton University Press, Princeton, NJ (1996)
Kaschiev, D.: Nucleation: Basic Theory with Applications. Butterworth-Heinemann, Oxford (2000)
Price, S.L.: Computed crystal energy landscapes for understanding and predicting organic crystal structures and polymorphism. Acc. Chem. Res. 42, 117–126 (2008)
Erdemir, D., Lee, A.Y., Myerson, A.S.: Nucleation of crystals from solution: classical and two-step models. Acc. Chem. Res. 42, 621–629 (2009)
Vekilov, P.G.: Nucleation. Cryst. Growth Des. 10, 5007–5019 (2010)
Auer, S., Frenkel, D.: Quantitative prediction of crystal-nucleation rates for spherical colloids: a computational approach. Annu. Rev. Phys. Chem. 55, 333–361 (2004)
Anwar, J., Zahn, D.: Uncovering molecular processes in crystal nucleation and growth by using molecular simulation. Angewandte Chemie-International Edition 50, 1996–2013 (2011)
Palmer, J.C., Debenedetti, P.G.: Recent advances in molecular simulation: a chemical engineering perspective. AIChE J. 61, 370–383 (2015)
TenWolde, P.R., RuizMontero, M.J., Frenkel, D.: Numerical calculation of the rate of crystal nucleation in a Lennard-Jones system at moderate undercooling. J. Chem. Phys. 104, 9932–9947 (1996)
Vehkamäki, H., Ford, I.J.: Critical cluster size and droplet nucleation rate from growth and decay simulations of Lennard-Jones clusters. J. Chem. Phys. 112, 4193–4202 (2000)
Auer, S., Frenkel, D.: Prediction of absolute crystal-nucleation rate in hard-sphere colloids. Nature 409, 1020–1023 (2001)
Moroni, D., ten Wolde, P.R., Bolhuis, P.G.: Interplay between structure and size in a critical crystal nucleus. Phys. Rev. Lett. 94, 235703 (2005)
Trudu, F., Donadio, D., Parrinello, M.: Freezing of a Lennard-Jones fluid: from nucleation to spinodal regime. Phys. Rev. Lett. 97, 105701 (2006)
Desgranges, C., Delhommelle, J.: Insights into the molecular mechanism underlying polymorph selection. J. Am. Chem. Soc. 128, 15104–15105 (2006)
Desgranges, C., Delhommelle, J.: Polymorph selection during the crystallization of Yukawa systems. J. Chem. Phys. 126, 054501 (2007)
Jungblut, S., Dellago, C.: Heterogeneous crystallization on tiny clusters. EPL (Europhysics Letters) 96, 56006 (2011)
Beckham, G.T., Peters, B.: Optimizing nucleus size metrics for liquid-solid nucleation from transition paths of near-nanosecond duration. J. Phys. Chem. Lett. 2, 1133–1138 (2011)
Chkonia, G., Wölk, J., Strey, R., Wedekind, J., Reguera, D.: Evaluating nucleation rates in direct simulations. J. Chem. Phys. 130, 064505 (2009)
Radhakrishnan, R., Trout, B.L.: Nucleation of hexagonal ice (Ih) in liquid water. J. Am. Chem. Soc. 125, 7743–7747 (2003)
Li, T., Donadio, D., Russo, G., Galli, G.: Homogeneous ice nucleation from supercooled water. Phys. Chem. Chem. Phys. 13, 19807–19813 (2011)
Reinhardt, A., Doye, J.P.K.: Free energy landscapes for homogeneous nucleation of ice for a monatomic water model. J. Chem. Phys. 136, 054501 (2012)
Sanz, E., Vega, C., Espinosa, J.R., Caballero-Bernal, R., Abascal, J.L.F., Valeriani, C.: Homogeneous ice nucleation at moderate supercooling from molecular simulation. J. Am. Chem. Soc. 135, 15008–15017 (2013)
Sear, R.P.: The non-classical nucleation of crystals: microscopic mechanisms and applications to molecular crystals, ice and calcium carbonate. Int. Mater. Rev. 57, 328–356 (2012)
Andrey, V.B., Jamshed, A., Ruslan, D., Richard, H.: Challenges in molecular simulation of homogeneous ice nucleation. J. Phys.: Condens. Matter 20, 494243 (2008)
Reinhardt, A., Doye, J.P.K.: Note: homogeneous TIP4P/2005 ice nucleation at low supercooling. J. Chem. Phys. 139, 096102 (2013)
Joswiak, M.N., Duff, N., Doherty, M.F., Peters, B.: Size-dependent surface free energy and tolman-corrected droplet nucleation of TIP4P/2005 water. J. Phys. Chem. Lett. 4, 4267–4272 (2013)
Holten, V., Limmer, D.T., Molinero, V., Anisimov, M.A.: Nature of the anomalies in the supercooled liquid state of the mW model of water. J. Chem. Phys. 138, 174501 (2013)
Valeriani, C., Sanz, E., Frenkel, D.: Rate of homogeneous crystal nucleation in molten NaCl. J. Chem. Phys. 122 (2005)
Quigley, D., Rodger, P.M.: Free energy and structure of calcium carbonate nanoparticles during early stages of crystallization. J. Chem. Phys. 128, 221101 (2008)
Li, T., Donadio, D., Galli, G.: Nucleation of tetrahedral solids: a molecular dynamics study of supercooled liquid silicon. J. Chem. Phys. 131, 224519 (2009)
Yi, P., Rutledge, G.C.: Molecular simulation of crystal nucleation in n-octane melts. J. Chem. Phys. 131, 134902 (2009)
Saika-Voivod, I., Poole, P.H., Bowles, R.K.: Test of classical nucleation theory on deeply supercooled high-pressure simulated silica. J. Chem. Phys. 124, 224709 (2006)
Agarwal, V., Peters, B.: Nucleation near the eutectic point in a Potts-lattice gas model. J. Chem. Phys. 140, 084111 (2014)
Singh, M., Dhabal, D., Nguyen, A.H., Molinero, V., Chakravarty, C.: Triplet correlations dominate the transition from simple to tetrahedral liquids. Phys. Rev. Lett. 112, 147801 (2014)
Shah, M., Santiso, E.E., Trout, B.L.: Computer simulations of homogeneous nucleation of benzene from the melt. J. Phys. Chem. B 115, 10400–10412 (2011)
Giberti, F., Salvalaglio, M., Mazzotti, M., Parrinello, M.: Insight into the nucleation of urea crystals from the melt. Chem. Eng. Sci. 121, 51–59 (2015)
Yu, T.-Q., Chen, P.-Y., Chen, M., Samanta, A., Vanden-Eijnden, E., Tuckerman, M.: Order-parameter-aided temperature-accelerated sampling for the exploration of crystal polymorphism and solid-liquid phase transitions. J. Chem. Phys. 140, 214109 (2014)
Samanta, A., Tuckerman, M.E., Yu, T.-Q.: E, W. Microscopic mechanisms of equilibrium melting of a solid. Science 346, 729–732 (2014)
Pedersen, U.R., Hummel, F., Dellago, C.: Computing the crystal growth rate by the interface pinning method. J. Chem. Phys. 142, 044104 (2015)
Maragliano, L., Fischer, A., Vanden-Eijnden, E., Ciccotti, G.: String method in collective variables: minimum free energy paths and isocommittor surfaces. J. Chem. Phys. 125, 024106 (2006)
Vanden-Eijnden, E., Venturoli, M.: Revisiting the finite temperature string method for the calculation of reaction tubes and free energies. J. Chem. Phys. 130, 194103 (2009)
Maragliano, L., Vanden-Eijnden, E., Roux, B.: Free energy and kinetics of conformational transitions from voronoi tessellated milestoning with restraining potentials. J. Chem. Theory Comput. 5, 2589–2594 (2009)
Vanden-Eijnden, E., Venturoli, M.: Markovian milestoning with Voronoi tessellations. J. Chem. Phys. 130, 194101 (2009)
Ovchinnikov, V., Karplus, M., Vanden-Eijnden, E.: Free energy of conformational transition paths in biomolecules: the string method and its application to myosin VI. J. Chem. Phys. 134, 085103 (2011)
Miller, T.F., III; Vanden-Eijnden, E., Chandler, D.: Solvent coarse-graining and the string method applied to the hydrophobic collapse of a hydrated chain. In: Proceedings of the National Academy of Sciences of the United States of America, vol. 104, pp. 14559–14564 (2007)
Santiso, E.E., Trout, B.L.: A general set of order parameters for molecular crystals. J. Chem. Phys. 134, 064109 (2011)
Santiso, E.E., Trout, B.L.: A general method for molecular modeling of nucleation from the melt. J. Chem. Phys. 143, 174109 (2015)
He, X., Shen, Y., Hung, F.R., Santiso, E.E.: Molecular simulation of homogeneous nucleation of crystals of an ionic liquid from the melt. J. Chem. Phys. 143, 124506 (2015)
Barducci, A., Bonomi, M., Parrinello, M.: Metadynamics. Wiley Interdis. Rev. Comput. Mol. Sci. 1, 826–843 (2011)
Allen, F.H.: The Cambridge structural database: a quarter of a million crystal structures and rising. Acta Crystallographica Sect. B-Struct. Sci. 58, 380–388 (2002)
Arduengo, A.J., Dias, H.V.R., Harlow, R.L., Kline, M.: Electronic stabilization of nucleophilic carbenes. J. Am. Chem. Soc. 114, 5530–5534 (1992)
Lopes, J.N.C., Deschamps, J., Padua, A.A.H.: Modeling ionic liquids using a systematic all-atom force field. J. Phys. Chem. B 108, 2038–2047 (2004)
Canongia Lopes, J.N., Padua, A.A.H.: Molecular force field for ionic liquids III: Imidazolium, pyridinium, and phosphonium cations; chloride, bromide, and dicyanamide anions. J. Phys. Chem. B 110, 19586–19592 (2006)
Lopes, J.N.C., Padua, A.A.H.: Molecular force field for ionic liquids composed of triflate or bistriflylimide anions. J. Phys. Chem. B 108, 16893–16898 (2004)
Shimizu, K., Almantariotis, D., Gomes, M.F.C., Padua, A.A.H., Lopes, J.N.C.: Molecular force field for ionic liquids V: hydroxyethylimidazolium, dimethoxy-2-methylimidazolium, and fluoroalkylimidazolium cations and bis(fluorosulfonyl)amide, perfluoroalkanesulfonylamide, and fluoroalkylfluorophosphate anions. J. Phys. Chem. B 114, 3592–3600 (2010)
Lopes, J.N.C., Padua, A.A.H., Shimizu, K.: Molecular force field for ionic liquids IV: trialkylimidazolium and alkoxycarbonyl-imidazolium cations; alkylsulfonate and alkylsulfate anions. J. Phys. Chem. B 112, 5039–5046 (2008)
Fannin, A.A., Floreani, D.A., King, L.A., Landers, J.S., Piersma, B.J., Stech, D.J., Vaughn, R.L., Wilkes, J.S., Williams, J.L.: Properties of 1,3-dialkylimidazolium chloride aluminum-chloride ionic liquids. 2. phase-transitions, densities, electrical conductivities, and viscosities. J. Phys. Chem. 88, 2614–2621 (1984)
Phillips, J.C., Braun, R., Wang, W., Gumbart, J., Tajkhorshid, E., Villa, E., Chipot, C., Skeel, R.D., Kale, L., Schulten, K.: Scalable molecular dynamics with NAMD. J. Comput. Chem. 26, 1781–1802 (2005)
Darden, T., York, D., Pedersen, L.: Particle mesh ewald—an n.log(n) method for ewald sums in large systems. J. Chem. Phys. 98, 10089–10092 (1993)
Hess, B., Bekker, H., Berendsen, H.J.C., Fraaije, J.: LINCS: A linear constraint solver for molecular simulations. J. Comput. Chem. 18, 1463–1472 (1997)
Vanden-Eijnden, E.: Some recent techniques for free energy calculations. J. Comput. Chem. 30, 1737–1747 (2009)
Pruppacher, H.R.: A new look at homogeneous ice nucleation in supercooled water drops. J. Atmos. Sci. 52, 1924–1933 (1995)
Taborek, P.: Nucleation in emulsified supercooled water. Phys. Rev. B 32, 5902–5906 (1985)
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).
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2016 Springer Science+Business Media Singapore
About this chapter
Cite this chapter
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
Download citation
DOI: https://doi.org/10.1007/978-981-10-1128-3_7
Published:
Publisher Name: Springer, Singapore
Print ISBN: 978-981-10-1126-9
Online ISBN: 978-981-10-1128-3
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)