3 research outputs found
Biodegradable Ionic Liquids: Effects of Temperature, Alkyl Side-Chain Length, and Anion on the Thermodynamic Properties and Interaction Energies As Determined by Molecular Dynamics Simulations Coupled with ab Initio Calculations
The
effects of incorporating the ester functional group (î—¸Cî—»OOî—¸)
into the side chain of the 1-alkyl-3-methylimidazolium cation ([C<sub>1</sub>COOC<sub><i>n</i></sub>C<sub>1</sub>im]<sup>+</sup>, <i>n</i> = 1, 2, 4) paired with [Br]<sup>−</sup>, [NO<sub>3</sub>]<sup>−</sup>, [BF<sub>4</sub>]<sup>−</sup>, [PF<sub>6</sub>]<sup>−</sup>, [TfO]<sup>−</sup>,
and [Tf<sub>2</sub>N]<sup>−</sup> anions on the various thermodynamic
properties and interaction energies of these biodegradable ionic liquids
(ILs) were investigated by means of molecular dynamics (MD) simulations
combined with ab initio calculations in the temperature range of 298–550
K. Excluding the simulated density, the highest values of the volumetric
properties such as molar volume, isobaric expansion coefficient, and
isothermal compressibility coefficient can be attributed to the largest
cation incorporated with the weakest coordinating anion, [Tf<sub>2</sub>N]<sup>−</sup>, and the minimum of the corresponding properties
correspond to the smallest cation, especially when combined with the
smaller anions, including [NO<sub>3</sub>]<sup>−</sup> and
[Br]<sup>−</sup>. In addition, ion-pair, cationic, and anionic
volumes were computed using MD simulations as well as ab initio calculations.
The results revelaed an increasing trend in the molar enthalpy of
vaporization. The reverse trends of the volumetric properties were
observed for the cohesive energy density, Hildebrand solubility parameter,
surface tension, surface excess enthalpy, lattice energy, thermal
pressure, internal pressure, binding energy, and interaction energy.
On the basis of the optimized structures, we believed that a reduction
in the strength of the hydrogen bonds due to the larger charge distribution
and steric hindrance of bulkier ions is responsible for the observed
trends. These results were also confirmed by calculating the critical
and boiling temperatures (by two different empirical equation), surface
excess enthalpies, parachors, and standard molar entropies. The other
derivatives of the thermodynamic properties such as the isobaric and
isochoric heat capacities, isothermal bulk moduli, and speeds of sound
in the ILs were computed as functions of temperature. Interestingly,
a direct relationship was found between the simulated results for
the surface tension and the computed values of the bulk modulus. Furthermore,
it was found that sound waves are transmitted faster in a compact
IL than in a compressible IL. In addition, for each IL, the molar
refraction, refractive index, dielectric constant, and mean static
polarizability were approximated at room temperature. The smallest
values of these properties were observed for ILs composed of the spherically
symmetric anions [PF<sub>6</sub>]<sup>−</sup> and [BF<sub>4</sub>]<sup>−</sup>. In addition, the formation of multiple intramolecular
hydrogen bonds between the O atoms of the ester functional group and
the hydrogen atoms of the cation was also observed for all optimized
conformations. Finally, the obtained results demonstrate that the
introduction of an ester group significantly increases the interionic
interactions and, subsequently, the packing efficiency of these ILs
in comparison with those of conventional imidazolium-based ILs
Hydroxyl-Functionalized 1‑(2-Hydroxyethyl)-3-methyl Imidazolium Ionic Liquids: Thermodynamic and Structural Properties using Molecular Dynamics Simulations and ab Initio Calculations
The
influences of hydroxyl functional group (−OH) on the thermodynamic
and structural properties of ionic liquids (ILs) composed of 1-(2-Hydroxyethyl)-3-methyl
imidazolium ([C<sub>2</sub>OHmim]<sup>+</sup>) cation and the six
different conventional anions, including [Cl]<sup>−</sup>,
[NO<sub>3</sub>]<sup>−</sup>, [BF<sub>4</sub>]<sup>−</sup>, [PF<sub>6</sub>]<sup>−</sup>, [TfO]<sup>−</sup>,
and [Tf<sub>2</sub>N]<sup>−</sup> have been extensively investigated
using classical molecular dynamics (MD) simulations combined with ab initio calculations over a wide range of temperature
(298–550 K). The volumetric thermodynamic properties, enthalpy
of vaporization, cohesive energy density, Hildebrand solubility parameter,
and heat capacity at constant pressure were estimated at desired temperature.
The simulated densities were in good agreement with the experimental
data with a slight overestimation. The interionic interaction of selected
ILs was also computed using both the MD simulations and ab initio calculations. It was found that the highest association
of cation and anion is attributed to [C<sub>2</sub>OHmim][Cl] followed by [C<sub>2</sub>OHmim][NO<sub>3</sub>], and [C<sub>2</sub>OHmim][Tf<sub>2</sub>N] with the bulkiest anion has the weakest interionic interaction among chosen ILs. The similar trend of interactions energies was nearly
observed from cohesive energy density results. Additional structural
details were comprehensively yielded by calculating radial distribution
functions (RDFs) and spatial distribution function (SDFs) at 358 K.
The most stable configurations of isolated and dimer ion pairs of
these ILs were in excellent consistency with RDFs and SDFs results.
Significant changes in arrangement of anions around the [C<sub>2</sub>OHmim]<sup>+</sup> cation in comparison with conventional imidazolium-based
ILs can be inferred from the MD simulations and ab initio results. Also, microscopic structural properties disclosed that
the most strong cation–cation interaction is ascribed to the
hydroxyl-functionalized ILs composed of bulkier anions, whereas ILs
incorporating [Cl]<sup>−</sup> and [NO<sub>3</sub>]<sup>−</sup> anions are mainly involved in cation–anion interactions.
The formation of the intramolecular hydrogen bonding in the [C<sub>2</sub>OHmim]<sup>+</sup> cation is another interesting result of
the present study
Molecular Dynamics and <i>ab Initio</i> Studies of the Effects of Substituent Groups on the Thermodynamic Properties and Structure of Four Selected Imidazolium-Based [Tf<sub>2</sub>N<sup>–</sup>] Ionic Liquids
All-atom molecular dynamics simulations
combined with <i>ab
initio</i> calculations are used to study the thermodynamic properties
and microscopic structure of four ionic liquids (ILs) based on the
imidazolium cation with different alkyl side branches, ([bmmim]<sup>+</sup>, 1-butyl-2,3-dimethylimidazolium; [bmim]<sup>+</sup>, 1-butyl-3-methylimidazolium;
[apmim]<sup>+</sup>, 1-(3-aminopropyl)-3-methylimidazolium; [mim]<sup>+</sup>, 1-methylimidazolium), paired with the [(CF<sub>3</sub>SO<sub>2</sub>)<sub>2</sub>N]<sup>−</sup>, bisÂ(trifluoromethanesulfonyl)Âimide
anion, in the temperature range of (298 to 600) K. We observed the
highest value of the molar internal energy, enthalpy of vaporization,
and cohesive energy density for the amine-functionalized [apmim]Â[Tf<sub>2</sub>N] ionic liquid. Structural analysis shows that the amine
functionalization of the end of the alkyl side chain of imidazolium
cation does not significantly affect the organization of [Tf<sub>2</sub>N]<sup>−</sup> around [apmim]<sup>+</sup>, but additional
NH<sub>2</sub> groups lead to short-range cation–cation structural
correlations between neighboring [apmim]<sup>+</sup>. The C2 methylation
extensively affects preferential out-of-plane face-to-face locations
of [Tf<sub>2</sub>N]<sup>−</sup> around [bmmim]<sup>+</sup> and also the cation–cation distributions. [mim]Â[Tf<sub>2</sub>N] has the highest simulated density and better packing efficiency
of liquid phase in comparison with other studied ILs. The strongest
first shell probability density region of [mim]<sup>+</sup> neighbors
above and below the imidazolium ring of the reference cation represents
better π–π stacking in the liquid phase of this
ionic liquid. The presented results determine the role of the cation
structure on the properties of this family of ILs. Good agreement
was achieved between simulation results of the bulk phase and quantum
calculations which are performed to determine the optimized structure
of isolated ion pairs in chosen configurations and the strength of
cation–anion interactions