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Title:CHARACTERIZATION OF INTERMOLECULAR INTERACTIONS AT PLAY IN THE 2,2,2-TRIFLUOROETHANOL TRIMERS USING CAVITY AND CHIRPED-PULSE MICROWAVE SPECTROSCOPY
Author(s):Seifert, Nathan A
Contributor(s):Xu, Yunjie; Jäger, Wolfgang; Thomas, Javix
Subject(s):Mini-symposium: Chirality-Sensitive Spectroscopy
Abstract:2,2,2-trifluoroethanol (TFE) is a common aqueous co-solvent in biological chemistry which may induce or destabilize secondary structures of proteins and polypeptides, thanks to its diverse intermolecular linkages originating from the hydrogen bonding potential of both the hydroxyl and perfluoro groups.footnote{M. Buck, Q. Rev. Biophys. 1998, 31, 297-335.} Theoretically, the TFE monomer is predicted to have two stable textit{gauche} (textit{gauche}$^{+}$/textit{gauche}$^{-}$) conformations whereas the textit{trans} form is unstable or is supported only by a very shallow potential. Only the gauche conformers have been identified in the gas phase, whereas liquid phase studies suggest a textit{trans}:textit{gauche} ratio of 2:3.footnote{I. Bakó, T. Radnai, M. Claire, B. Funel, J. Chem. Phys. 2004, 121, 12472-12480. } The question at which sample (cluster) size the textit{trans} form of TFE would appear was one major motivation for our study.\_x000d_ _x000d_ Here, we report the detection of three trimers of TFE using Balle-Flygare cavity and chirped-pulse Fourier transform microwave spectroscopy (CP-FTMW) techniques. The most stable observed trimer features one textit{trans}- and two textit{gauche}-TFE subunits. The other two trimers, observed using a newly constructed 2-6 GHz CP-FTMW spectrometer, consist of only the two textit{gauche} conformers of TFE. Quantum Theory of Atoms in Molecules (QTAIM)footnote{R. F. W. Bader, Chem. Rev. 1991, 91, 893-928.} and non-covalent interactions (NCI)footnote{E. R. Johnson, S. Keinan, P. Mori-Sánchez, J. Contreras-Garcia, A. J. Cohen, W. Yang, J. Am. Chem. Soc., 2010, 132, 6498-6506.} analyses give detailed insights into which intermolecular interactions are at play to stabilize the textit{trans} form of TFE in the most stable trimer.
Issue Date:6/22/2017
Publisher:International Symposium on Molecular Spectroscopy
Citation Info:APS
Genre:CONFERENCE PAPER/PRESENTATION
Type:Text
Language:English
URI:http://hdl.handle.net/2142/97114
DOI:10.15278/isms.2017.RG06
Date Available in IDEALS:2017-07-27


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