Effect of alkyl-group flexibility on the melting point of imidazolium-based ionic liquids

Bernardino, Kalil; Zhang, Yong; Ribeiro, Mauro C. C.; Maginn, Edward J.

doi:10.1063/5.0015992

Cited by 27 publications

(16 citation statements)

References 51 publications

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“…For example, several groups used MD simulations with articial, deliberate changes in the dihedral parameters to increase the barriers for rotation around specic bonds, thus separating out the effects of conformational exibility. [183][184][185][186] Despite the astounding successes of classical MD simulations, one of the central problems remains the choice of a force eld, i.e. the rst step in Fig.…”

Section: Machine Learning For Molecular Dynamics Simulationsmentioning

confidence: 99%

A review on machine learning algorithms for the ionic liquid chemical space

et al. 2021

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Section: Machine Learning For Molecular Dynamics Simulationsmentioning

confidence: 99%

A review on machine learning algorithms for the ionic liquid chemical space

et al. 2021

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“…Melting temperature of [dIqu][PF 6 ], being 308.9 K, is significantly lower than the results that a simple correlation with its cohesive energy would yield. A long side n -decyl chain of the cation probably brings a large entropy contribution to the solid–liquid equilibrium in this case . An opposite outlier in terms of T fus is represented by [emPyrr][NTf 2 ], whose experimental T fus is significantly larger than it would result only from its cohesive energy.…”

Section: Results and Discussionmentioning

confidence: 94%

“…A long side ndecyl chain of the cation probably brings a large entropy contribution to the solid−liquid equilibrium in this case. 110 An opposite outlier in terms of T fus is represented by [emPyrr]-[NTf 2 ], whose experimental T fus is significantly larger than it would result only from its cohesive energy. It is also interesting that [emPyrr][NTf 2 ] is one of the two IL crystals originally collapsing in CL&P-D k simulations at its large experimental T fus .…”

Section: Resultsmentioning

confidence: 99%

Does Explicit Polarizability Improve Simulations of Phase Behavior of Ionic Liquids?

Klajmon

Červinka

2021

J. Chem. Theory Comput.

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Molecular dynamics simulations are performed for a test set of 20 aprotic ionic liquids to investigate whether including an explicit polarizability model in the force field leads to higher accuracy and reliability of the calculated phase behavior properties, especially the enthalpy of fusion. A classical nonpolarizable all-atom optimized potentials for liquid simulations (OPLS) force-field model developed by Canongia Lopes and Padua (CL&P) serves as a reference level of theory. Polarizability is included either in the form of Drude oscillators, resulting in the CL&P-D models, or in the framework of the atomic multipole optimized energetics for biomolecular application (AMOEBA) force field with polarizable atomic sites. Benchmarking of the calculated fusion enthalpy values against the experimental data reveals that overall the nonpolarizable CL&P model and polarizable CL&P-D models perform similarly with average deviations of about 30%. However, fusion enthalpies from the CL&P-D models exhibit a stronger correlation with their experimental counterparts. The least successful predictions are interestingly obtained from AMOEBA (deviation ca. 60%), which may indicate that a reparametrization of this forcefield model is needed to achieve improved predictions of the fusion enthalpy. In general, all FF models tend to underestimate the fusion enthalpies. In addition, quantum chemical calculations are used to compute the electronic cohesive energies of the crystalline phases of the ionic liquids and of the interaction energies within the ion pair. Significant positive correlations are found between the fusion enthalpy and the cohesive energies. The character of the present anions predetermines the magnitude of individual mechanistic components of the interaction energy and related enthalpic and cohesive properties.

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“…To perform the D fus S decomposition, we have developed a computational protocol using classical molecular dynamics (MD) simulations (see the ESI † for details). D fus S and D confor S were estimated from the thermodynamic integration 15,16 and conformational analyses, respectively. We employed the twophase thermodynamic (2PT) approach, initially developed by Lin et al, for the kinetic entropy estimations.…”

Section: Fusion Entropy Decompositionmentioning

confidence: 99%