No abstract

Liquid structures of the bis(trifluoromethanesulfonyl)amide based ionic liquids composed of 1-ethyl-3-methylimidazolium and N-methyl-N-propylpyrrolidinium ([C(2)mIm(+)][TFSA(-)] and [C(3)mPyrro(+)][TFSA(-)], respectively) and Li(+) ion solvation structure in their lithium salt solutions were studied by means of high-energy X-ray diffraction (HEXRD) technique with the aid of MD simulations. With regard to neat ionic liquids, a small but significant difference was found at around 3.5 Å in the intermolecular radial distribution functions G(inter)(r)s for these two ionic liquids; i.e., G(inter)(r) for [C(2)mIm(+)][TFSA(-)] was positioned at a slightly shorter region relative to that for [C(3)mPyrro(+)][TFSA(-)], which suggests that the nearest neighboring cation-anion interaction in the imidazolium ionic liquid is slightly greater than that in the other. With regard to Li(+) ion solvation structure, G(inter)(r)s for [C(2)mIm(+)][TFSA(-)] dissolving Li(+) ion exhibited additional small peak of about 1.9 Å attributable to the Li(+)-O (TFSA(-)) atom-atom correlation, though the corresponding peak was unclear in [C(3)mPyrro(+)][TFSA(-)] due to overlapping with the intramolecular atom-atom correlations in [C(3)mPyrro(+)]. In addition, the long-range density fluctuation observed in the neat ionic liquids diminished with the increase of Li(+) ion concentration for both ionic liquid solutions. These observations indicate that the large scale Li(+) ion solvated clusters are formed in the TFSA based ionic liquids, and well support the formation of [Li(TFSA)(2)](+) cluster clarified by previous Raman spectroscopic studies. MD simulations qualitatively agree with the experimental facts, by which the decrease in the long-range oscillation amplitude of r(2){G(r) - 1} for the Li(+) containing ionic liquids can be ascribed to the variation in the long-range anion-anion correlations caused by the formation of the Li(+) ion solvated clusters.

Liquid structure and the closest ion-ion interactions in a series of primary alkylammonium nitrate ionic liquids [C(n)Am(+)][NO(3)(-)] (n = 2, 3, and 4) were studied by means of high-energy X-ray diffraction (HEXRD) experiments with the aid of molecular dynamics (MD) simulations. Experimental density and X-ray structure factors are in good accordance with those evaluated with MD simulations. With regard to liquid structure, characteristic peaks appeared in the low Q (Q: a scattering vector) region of X-ray structure factors S(Q)'s for all ionic liquids studied here, and they increased in intensity with a peak position shift toward the lower Q side by increasing the alkyl chain length. Experimentally evaluated S(Q(peak))(r(max)) functions, which represent the S(Q) intensity at a peak position of maximum intensity Q(peak) as a function of distance (actually a integration range r(max)), revealed that characteristic peaks in the low Q region are related to the intermolecular anion-anion correlation decrease in the r range of 10-12 Å. Appearance of the peak in the low Q region is probably related to the exclusion of the correlations among ions of the same sign in this r range by the alkyl chain aggregation. From MD simulations, we found unique and rather distorted NH···O hydrogen bonding between C(n)Am(+) (n = 2, 3, and 4) and NO(3)(-) in these ionic liquids regardless of the alkyl chain length. Subsequent ab initio calculations for both a molecular complex C(2)H(5)NH(2)···HONO(2) and an ion pair C(2)H(5)NH(3)(+)···ONO(2)(-) revealed that such distorted hydrogen bonding is specific in a liquid state of this family of ionic liquids, though the linear orientation is preferred for both the N···HO hydrogen bonding in a molecular complex and the NH···O one in an ion pair. Finally, we propose our interpretation of structural heterogeneity in PILs and also in APILs.

Molecular dynamics simulations in slab geometry and surface tension measurements were performed for aqueous solutions of magnesium acetate and magnesium nitrate at various concentrations. The simulations reveal a strong affinity of acetate anions for the surface, while nitrate exhibits only a very weak surface propensity, and magnesium is per se strongly repelled from the air/water interface. CH3COO- also exhibits a much stronger tendency than NO3- for ion pairing with Mg2+ in the bulk and particularly in the interfacial layer. The different interfacial behavior of the two anions is reflected by the opposite concentration dependence (beyond 0.5 M) of surface tension of the corresponding magnesium salts. Measurements, supported by simulations, show that the surface tension of Mg(NO3)2(aq) increases with concentration as for other inorganic salts. However, in the case of Mg(OAc)2(aq) the surface tension isotherm exhibits a turnover around 0.5 M, after which it starts to decrease, indicating a positive net solute excess in the interfacial layer at higher concentrations.