Are There Magic Compositions in Deep Eutectic Solvents? Effects of Composition and Water Content in Choline Chloride/Ethylene Glycol from Ab Initio Molecular Dynamics

Alizadeh, Vahideh; Malberg, Friedrich; Pádua, Agı́lio A. H.; Kirchner, Barbara

doi:10.1021/acs.jpcb.0c04844

Cited by 106 publications

(105 citation statements)

References 83 publications

(120 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The interactions between the cation and the HBD are not marked, as shown in Figure 7. These results are in agreement with a recent ab-initio MD study, 72 even though the intensities of certain peaks do not coincide perfectly, as can be expected due to the small sizes and duration sof AIMD trajectories, as well as the obvious differences in the Hamiltonian. good accord between two methods for Cl -• • • Ch + correlations, while the intensity for EG is lower from our force field when compared to AIMD, which could be related to faster diffusion of the HBD discussed above.…”

Section: B Modification Of Atomic Diameterssupporting

confidence: 90%

Extension of the CL&Pol Polarizable Force Field to Electrolytes, Protic Ionic Liquids, and Deep Eutectic Solvents

Goloviznina

Gong

Gomes

et al. 2021

J. Chem. Theory Comput.

Self Cite

114

View full text Add to dashboard Cite

is extended to electrolytes, protic ionic liquids, deep eutectic solvents, and glycols. These systems are problematic in polarizable simulations because they contain either small, highly charged ions or strong hydrogen bonds, which cause trajectory instabilities due to the pull exerted on the induced dipoles. We use a Tang-Toennies function to dampen, or smear, the interactions between charges and induced dipole at short range involving small, highly charged atoms (such as hydrogen or lithium), thus preventing the "polarization catastrophe". The new force field gives stable trajectories and is validated through comparison with experimental data on density, viscosity, and ion diffusion coefficients of liquid systems of the above-mentioned classes. The results also shed light on the hydrogen-bonding pattern in ethylammonium nitrate, a protic ionic liquid, for which the literature contains conflicting views. We describe the implementation of the Tang-Toennies damping function, of the temperature-grouped Nosé-Hoover thermostat for polarizable molecular dynamics and of the periodic perturbation method for viscosity evaluation from non-equilibrium trajectories in the LAMMPS molecular dynamics code. The main result of this work is the wider applicability of the CL&Pol polarizable force field to new, important classes of fluids, achieving robust trajectories and a good description of equilibrium and transport properties in challenging systems. The fragment-based approach of CL&Pol will allow ready extension to a wide variety of protic ionic liquids, deep eutectic solvents and electrolytes.

show abstract

Section: B Modification Of Atomic Diameterssupporting

confidence: 90%

Extension of the CL&Pol Polarizable Force Field to Electrolytes, Protic Ionic Liquids, and Deep Eutectic Solvents

Goloviznina

Gong

Gomes

et al. 2021

J. Chem. Theory Comput.

Self Cite

114

View full text Add to dashboard Cite

show abstract

“…The interactions between the cation and the HBD are not marked, as shown in Figure 6. These results are in agreement with a recent ab-initio MD study, 65 even though the intensities of certain peaks do not coincide perfectly. In particular, the height of the first peak Clwith EG is underestimated by the Cl&Pol force field when compared to the AIMD, and this could be related to faster diffusion of the HBD discussed above.…”

Section: The H • • • a Distances And The D H • • • A Angles (Where A supporting

confidence: 88%

Transferable, Polarizable Force Field for Electrolytes, Protic Ionic Liquids and Deep Eutectic Solvents

Pádua

Goloviznina²,

Gomes³

et al. 2020

Preprint

Self Cite

View full text Add to dashboard Cite

The transferable, polarizable CL&Pol force field for aprotic ionic liquids presented in our previous study (J. Chem. Theory Comput. 2019, 15, 5858, DOI: 10.1021/acs.jctc.9b00689) is extended to electrolytes, protic ionic liquids, deep eutectic solvents, and glycols. These systems are problematic in polarizable simulations because they contain either small, highly charged ions or strong hydrogen bonds, which cause trajectory instabilities due to the pull exerted on the induced dipoles. We use a Tang-Toennies function to dampen, or smear, the interactions between charges and induced dipole at short range involving small, highly charged atoms (such as hydrogen or lithium), thus preventing the "polarization catastrophe". The new force field gives stable trajectories and is validated through comparison with experimental data on density, viscosity, and ion diffusion coefficients of liquid systems of the above-mentioned classes. The results also shed light on the hydrogen-bonding pattern in ethylammonium nitrate, a protic ionic liquid, for which the literature contains conflicting views. We describe the implementation of the Tang-Toennies damping function, of the temperature-grouped Nosé-Hoover thermostat for polarizable molecular dynamics and of the periodic perturbation method for viscosity evaluation from non-equilibrium trajectories in the LAMMPS molecular dynamics code. The main result of this work is the wider applicability of the CL&Pol polarizable force field to new, important classes of fluids, achieving robust trajectories and a good description of equilibrium and transport properties in challenging systems. The transferability and fragment-based approach of CL&Pol will allow ready extension to a wide variety of protic ionic liquids, deep eutectic solvents and electrolytes.

show abstract

“…All the DES used in this work have a higher density than the pure HBD used in their preparation and at a fixed temperature, the density increases with a higher molar fraction of the HBA. Other workers 45,46 have shown that the DES in general exhibit a non ideal behavior. For the systems studied in this work we cannot confirm this finding as the density of solid choline chloride has not been reported in literature and the first derivative of molar volume remains constant over the limited range of mole fractions studied.…”

Section: Density and Viscosity Measurementsmentioning

confidence: 96%

Viscosity of Choline Chloride-Based Deep Eutectic Solvents: Experiments and Modeling

et al. 2020

View full text Add to dashboard Cite

Deep eutectic solvents (DES) have emerged as promising 'green' solvents, but their successful industrial application requires relatively low viscosity. DES prepared from choline chloride and glycols offer such possibility. Viscosity and density are reported for a number of DES obtained by mixing choline chloride and a glycol (ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,4-butanediol). The measurements were performed at 101.3 kPa, at temperatures between 293.15 K and 333.15 K, and for different mole ratios of the glycol and choline chloride. The viscosity was measured with a capillary viscometer, while the density was measured by means of a vibrating U-tube densimeter. The density and viscosity data have expanded relative uncertainties of 0.2% and 2.0%, respectively, with a coverage factor of 2. The viscosity of pure glycols was modeled using the extended hard-sphere (EHS) model that has its basis in kinetic theory and the molecular description of the fluid. Each DES was treated as a binary mixture, and the EHS model was used, with a mole average mixing rule, to calculate its viscosity. The measured DES viscosity data were represented with the average absolute deviation of 1.4% and a maximum deviation of 7%.

show abstract

Are There Magic Compositions in Deep Eutectic Solvents? Effects of Composition and Water Content in Choline Chloride/Ethylene Glycol from Ab Initio Molecular Dynamics

Cited by 106 publications

References 83 publications

Extension of the CL&Pol Polarizable Force Field to Electrolytes, Protic Ionic Liquids, and Deep Eutectic Solvents

Extension of the CL&Pol Polarizable Force Field to Electrolytes, Protic Ionic Liquids, and Deep Eutectic Solvents

Transferable, Polarizable Force Field for Electrolytes, Protic Ionic Liquids and Deep Eutectic Solvents

Viscosity of Choline Chloride-Based Deep Eutectic Solvents: Experiments and Modeling

Contact Info

Product

Resources

About