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Title: Spectroscopic and computational analysis of the molecular interactions in the ionic liquid ion pair [BMP]+[TFSI]-

Abstract

1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([BMP]{sup +}[TFSI]{sup -}) ion pairs were studied using DFT at the B3LYP/6-31 + G(d) level. Nine locally stable conformations of the ion pair were located. In the most stable conformation, [TFSI]{sup -} takes a cis conformation and lies below the pyrrolidinium ring. Atoms-in-molecules (AIM) and electron density analysis indicated the existence of nine hydrogen bonds. Interaction energies were recalculated at the Second-order Møller–Plesset (MP2) level to show the importance of dispersion interaction. Further investigation through natural bond orbital (NBO) analysis provided insight into the importance of charge transfer interactions in the ion pair. Harmonic vibrations of the ion pair were calculated and compared with vibrations of the free ions as well as the experimental infrared spectrum. Assignments and frequency shifts are discussed in light of the inter-ionic interactions.

Authors:
; ; ;
Publication Date:
Research Org.:
National Energy Technology Lab. (NETL), Pittsburgh, PA, and Morgantown, WV (United States). In-house Research
Sponsoring Org.:
USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1129545
Report Number(s):
A-UNIV-PUB-031
Journal ID: ISSN 0167-7322
DOE Contract Number:  
DE-FE0004000
Resource Type:
Journal Article
Journal Name:
Journal of Molecular Liquids
Additional Journal Information:
Journal Volume: 175; Journal Issue: C; Journal ID: ISSN 0167-7322
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ionic liquids; Density functional theory; [BMP]+[TFSI]−; Infrared spectroscopy; NBO AIM

Citation Formats

Mao, James X., Nulwala, Hunaid B., Luebke, David R., and Damodaran, Krishnan. Spectroscopic and computational analysis of the molecular interactions in the ionic liquid ion pair [BMP]+[TFSI]-. United States: N. p., 2012. Web. doi:10.1016/j.molliq.2012.09.001.
Mao, James X., Nulwala, Hunaid B., Luebke, David R., & Damodaran, Krishnan. Spectroscopic and computational analysis of the molecular interactions in the ionic liquid ion pair [BMP]+[TFSI]-. United States. doi:10.1016/j.molliq.2012.09.001.
Mao, James X., Nulwala, Hunaid B., Luebke, David R., and Damodaran, Krishnan. Thu . "Spectroscopic and computational analysis of the molecular interactions in the ionic liquid ion pair [BMP]+[TFSI]-". United States. doi:10.1016/j.molliq.2012.09.001.
@article{osti_1129545,
title = {Spectroscopic and computational analysis of the molecular interactions in the ionic liquid ion pair [BMP]+[TFSI]-},
author = {Mao, James X. and Nulwala, Hunaid B. and Luebke, David R. and Damodaran, Krishnan},
abstractNote = {1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([BMP]{sup +}[TFSI]{sup -}) ion pairs were studied using DFT at the B3LYP/6-31 + G(d) level. Nine locally stable conformations of the ion pair were located. In the most stable conformation, [TFSI]{sup -} takes a cis conformation and lies below the pyrrolidinium ring. Atoms-in-molecules (AIM) and electron density analysis indicated the existence of nine hydrogen bonds. Interaction energies were recalculated at the Second-order Møller–Plesset (MP2) level to show the importance of dispersion interaction. Further investigation through natural bond orbital (NBO) analysis provided insight into the importance of charge transfer interactions in the ion pair. Harmonic vibrations of the ion pair were calculated and compared with vibrations of the free ions as well as the experimental infrared spectrum. Assignments and frequency shifts are discussed in light of the inter-ionic interactions.},
doi = {10.1016/j.molliq.2012.09.001},
journal = {Journal of Molecular Liquids},
issn = {0167-7322},
number = C,
volume = 175,
place = {United States},
year = {2012},
month = {11}
}