Interaction between ionic liquid cation and water: infrared predissociation study of [bmim]+·(H2O)n clusters

Literature Information

Publication Date 2016-06-29
DOI 10.1039/C6CP02730J
Impact Factor 3.676
Authors

Jonathan M. Voss, Brett M. Marsh, Jia Zhou, Etienne Garand


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Abstract

The infrared predissociation spectra of [bmim]+·(H2O)n, n = 1–8, in the 2800–3800 cm−1 region are presented and analyzed with the help of electronic structure calculations. The results show that the water molecules solvate [bmim]+ by predominately interacting with the imidazolium C2–H moiety for the small n = 1 and 2 clusters. This is characterized by a redshifted and relatively intense C2–H stretch. For n ≥ 4 clusters, hydrogen-bond interactions between the water molecules drive the formation of ring isomers which interact on top of the imidazolium ring without any direct interaction with the C2–H. The water arrangement in [bmim]+·(H2O)n is similar to the low energy isomers of neutral water clusters up to the n = 6 cluster. This is not the case for the n = 8 cluster, which has the imidazolium ring disrupting the otherwise preferred cubic water structure. The evolution of the solvation network around [bmim]+ illustrates the competing [bmim]+–water and water–water interactions.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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