Send to

Choose Destination
See comment in PubMed Commons below
J Phys Chem B. 2012 Mar 8;116(9):2801-13. doi: 10.1021/jp209561t. Epub 2012 Feb 29.

Structural heterogeneity and unique distorted hydrogen bonding in primary ammonium nitrate ionic liquids studied by high-energy X-ray diffraction experiments and MD simulations.

Author information

Department of Chemistry, Faculty of Science, Kyushu University, Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan.


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.

PubMed Commons home

PubMed Commons

How to join PubMed Commons

    Supplemental Content

    Full text links

    Icon for American Chemical Society
    Loading ...
    Support Center