Raman spectra of 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)amide [C 2 mIm + ][FSA − ] ionic liquid solutions dissolving LiFSA salt of various concentrations were measured at 298 K. FSA − ((FSO 2 ) 2 N − ) is an analogue anion of bis(trifluoromethanesulfonyl)amide ((CF 3 SO 2 ) 2 N − ; TFSA − ). We found that a solvation number of the Li + ion in [C 2 mIm + ][FSA − ] is 3, though it has been well established that Li + ion is solvated by two TFSA − anions in the corresponding ionic liquids below the Li + ion mole fraction of x Li + < 0.2. To yield further insight into larger solvation numbers, Raman spectra were measured at higher temperatures up to 364 K. The Li + ion solvation number in [C 2 mIm + ][FSA − ] evidently decreased when the temperature was elevated. Temperature dependence of the Li + ion solvation number was analyzed assuming an equilibrium between [Li(FSA) 2 ] − and [Li(FSA) 3 ] 2− , and the enthalpy ΔH°and the temperature multiplied entropy TΔS°for one FSA − liberation toward a bulk ionic liquid were successfully evaluated to be 35(2) kJ mol −1 and 29(2) kJ mol −1 , respectively. The ΔH°and ΔS°suggest that the Li + ion is coordinated by one of bidentate and two of monodentate FSA − at 298 K, and that the more weakly solvated monodentate FSA − is liberated at higher temperatures. The high-energy X-ray diffraction (HEXRD) experiments of these systems were carried out and were analyzed with the aid of molecular dynamics (MD) simulations. In radial distribution functions evaluated with HEXRD, a peak at about 1.94 Å appeared and was attributable to the Li + −O(FSA − ) correlations. The longer Li + −O(FSA − ) distance than that for the Li + −O(TFSA − ) of 1.86 Å strongly supports the larger solvation number of the Li + ions in the FSA − based ionic liquids. MD simulations at least qualitatively reproduced the Raman and HEXRD experiments.

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.

Poly(dibutylstannane) and poly(dioctylstannane) were obtained by electrochemical polymerization of dibutyldichlorostannane and dioctyldichlorostannane, respectively, in a one-compartment cell equipped with a platinum cathode and a silver anode, using tetrabutylammonium perchlorate and DME as the supporting electrolyte and the solvent, respectively.

We constructed a Japanese garden on the rooftop of a hospital in Japan and assessed with a total of 25 subjects on the following categories: (1) eye movement, (2) heart rate, and (3) behavior under four different conditions: (a) open view of the site before construction of the Japanese garden (the control space), (b) open view of the Japanese garden, (c) view of the Japanese garden through closed door, and (d) view of Japanese garden through closed door with the chrysanthemum scent. Findings/Results: Viewers' eyes scanned larger area while viewing the Japanese garden, and viewing the Japanese garden significantly reduced heart rate and improved behavioral symptoms than the control space. We also found that the effect of viewing the same Japanese garden differed across three conditions: the view through an open door, a closed door, and a closed door with added scent.