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 ([C2OHmim](+)) cation and the six different conventional anions, including [Cl](-), [NO3](-), [BF4](-), [PF6](-), [TfO](-), and [Tf2N](-) 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 [C2OHmim][Cl] followed by [C2OHmim][NO3], and [C2OHmim][Tf2N] 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 [C2OHmim](+) 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](-) and [NO3](-) anions are mainly involved in cation-anion interactions. The formation of the intramolecular hydrogen bonding in the [C2OHmim](+) cation is another interesting result of the present study.

Molecular dynamics simulations of four ionic liquids (ILs) based on the [Tf 2 N] − , bis(trifluoromethanesulfonyl)imide anion, and imidazolium cations with different alkyl side chains have been performed. These simulations investigate the influence of butyl side chain elimination, tail amine functional addition, and C2 methylation on the dynamics and transport properties of this family of ionic liquids at 400 K. In our earlier work (J. Chem. Eng. Data, 2014, 59, 2834−2849), a suite of thermodynamic quantities and microscopic structures of these ILs were studied by classical molecular dynamics simulations and ab initio calculations. In this work, the dynamics of the ILs are studied by calculating the mean-square displacement (MSD) and the velocity autocorrelation function (VACF) for selected atomic sites and the centers of mass of the ions. These results are used to calculate the self-diffusion and the ionic conductivity from both the Einstein and Green−Kubo formulas. The calculated ionic self-diffusion coefficients are used to estimate the cationic transference number and the Stokes−Einstein viscosity for the four ILs. In agreement with experiments, the general simulated trends in the MSD, self-diffusion, and ionic conductivity are [bmim][Tf 2 N] > [apmim][Tf 2 N] > [bmmim][Tf 2 N] > [mim][Tf 2 N]. These trends are the reverse of the trend in the viscosity of four selected ILs. As expected by applying a nonpolarizable force field, the simulation results tend to underestimate the self-diffusivity and conductivity, and overestimate the shear viscosity. The highest and the lowest degrees of ionic association are detected for [mim][Tf 2 N] and [bmim][Tf 2 N], respectively.

The effects of incorporating the ester functional group (COO) into the side chain of the 1-alkyl-3methylimidazolium cation ([C 1 COOC n C 1 im] + , n = 1, 2, 4) paired with [Br] − , [NO 3 ] − , [BF 4 ] − , [PF 6 ] − , [TfO] − , and [Tf 2 N] − 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 2 N] − , and the minimum of the corresponding properties correspond to the smallest cation, especially when combined with the smaller anions, including [NO 3 ] − and [Br] − . 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 6 ] − and [BF 4 ] − . 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.

The effects of ester addition on nanostructural properties of biodegradable ILs composed of 1-alkoxycarbonyl-3-alkyl-imidazolium cations ([C1COOCnC1im](+), n = 1, 2, 4) combined with [Br](-), [NO3](-), [BF4](-), [PF6](-), [TfO](-), and [Tf2N](-) were explored by using the molecular dynamics (MD) simulations and quantum theory of atoms in molecules (QTAIM) analysis at 400 K. Various thermodynamic properties of these ILs were extensively computed in our earlier work (Ind. Eng. Chem. Res., 2015, 54, 11678-11700). Nano-scale segregation analysis demonstrates the formation of a small spherical island-like hydrocarbon within the continuous ionic domain for ILs with short alkyl side chain ([C1COOC1C1im]), and a sponge-like nanostructure for the compound with long alkyl side chain ([C1COOC4C1im]). Ester-functionalized ILs with ethyl side chain ([C1COOC2C1im]) are the turning point between two different morphologies. Non-polar channels were observed for [C1COOC4C1im] ILs composed of smaller anions such as [Br] and [NO3], whereas clustering organization was found for the other anions. Formation of the spherical micelle-like nanostructure was seen for lengthened cations. Finally, the incorporation of an ester group into the alkyl side chain of the cation leads to stronger segregation between charged and uncharged networks, which consequently increased the possibility of self-assembly and micelle formation.

All-atom molecular dynamics simulations combined with ab initio 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] + , 1-butyl-2,3-dimethylimidazolium; [bmim] + , 1-butyl-3-methylimidazolium; [apmim] + , 1-(3-aminopropyl)-3-methylimidazolium; [mim] + , 1-methylimidazolium), paired with the [(CF 3 SO 2 ) 2 N] − , bis-(trifluoromethanesulfonyl)imide 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][Tf 2 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 2 N] − around [apmim] + , but additional NH 2 groups lead to short-range cation−cation structural correlations between neighboring [apmim] + . The C2 methylation extensively affects preferential out-of-plane face-toface locations of [Tf 2 N] − around [bmmim] + and also the cation−cation distributions. [mim][Tf 2 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] + 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.