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Title: Interaction between ionic liquid cation and water: Infrared predissociation study of [bmim] +·(H 2O) n clusters

The infrared predissociation spectra of [bmim] +·(H 2O) 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]+·(H 2O) 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. Here, the evolution of the solvation network around [bmim]+ illustrates the competing [bmim]+–water and water–water interactions.
Authors:
 [1] ;  [1] ;  [1] ;  [1]
  1. Univ. of Wisconsin, Madison, WI (United States)
Publication Date:
Grant/Contract Number:
SC0010326
Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 18; Journal Issue: 28; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Research Org:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1358403

Voss, Jonathan M., Marsh, Brett M., Zhou, Jia, and Garand, Etienne. Interaction between ionic liquid cation and water: Infrared predissociation study of [bmim]+·(H2O)n clusters. United States: N. p., Web. doi:10.1039/c6cp02730j.
Voss, Jonathan M., Marsh, Brett M., Zhou, Jia, & Garand, Etienne. Interaction between ionic liquid cation and water: Infrared predissociation study of [bmim]+·(H2O)n clusters. United States. doi:10.1039/c6cp02730j.
Voss, Jonathan M., Marsh, Brett M., Zhou, Jia, and Garand, Etienne. 2016. "Interaction between ionic liquid cation and water: Infrared predissociation study of [bmim]+·(H2O)n clusters". United States. doi:10.1039/c6cp02730j. https://www.osti.gov/servlets/purl/1358403.
@article{osti_1358403,
title = {Interaction between ionic liquid cation and water: Infrared predissociation study of [bmim]+·(H2O)n clusters},
author = {Voss, Jonathan M. and Marsh, Brett M. and Zhou, Jia and Garand, Etienne},
abstractNote = {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. Here, the evolution of the solvation network around [bmim]+ illustrates the competing [bmim]+–water and water–water interactions.},
doi = {10.1039/c6cp02730j},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 28,
volume = 18,
place = {United States},
year = {2016},
month = {6}
}

Works referenced in this record:

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005
  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a