Paper Citing NAMD - Abstract
MacMillan, Amanda C.; McIntire, Theresa M.; Freites, J. Alfredo; Tobias, Douglas J.; Nizkorodov, Sergey A.
Interaction of Water Vapor with the Surfaces of Imidazolium-Based Ionic Liquid Nanoparticles and Thin Films
JOURNAL OF PHYSICAL CHEMISTRY B, 116:11255-11265, SEP 13 2012
Understanding the interactions of humid air with ionic liquids (ILs) is critical for predicting how their physicochemical properties are affected by water. Using experimental and theoretical techniques, water vapor's interaction with aerosolized nanoparticles and thin films of [C2MIM][Cl] and [C2MIM][BF4] was studied. Solutions were electrosprayed to produce dry particles. Particles' hygroscopic growth was quantified using tandem nanodifferential mobility analysis as a function of relative humidity (RH). This is the first report of the interaction of water with aerosolized IL nanoparticles. The particles' small size allows true IL-water vapor equilibrium achieved quickly. Growth curves for both ILs show steady water uptake with increasing RH. Water vapor uptake by IL thin films was also examined using ATR-FTIR spectroscopy. Both experimental methods show [C2MIM][Cl] absorbs more water vapor than [C2MIM][BF4] over the entire RH range. Water molar fractions, calculated from growth curves, agreed well with those estimated from ATR-FTIR data. MD simulations, used to model IL-water interactions, revealed strong interactions between [Cl-] and water and considerably weaker interactions between [BF4-] and water. Widths and position of O-H stretching vibrations from MD simulations qualitatively reproduced ATR-FTIR results. These experimental and theoretical data provide a comprehensive picture of the behavior of absorbed water in ILs.
