Bracketing subtle conformational energy differences between self-solvated and stretched trifluoropropanol.
2015-04-21 | journal article. A publication of Göttingen
Jump to: Cite & Linked | Documents & Media | Details | Version history
Documents & Media
c4cp05868b.pdf2.77 MBAdobe PDFSupplemantary Information1.05 MBAdobe PDFc4cp05868b.pdf2.77 MBUnknownSupplemantary Information1.05 MBUnknown
Details
- Authors
- Heger, Matthias; Otto, Katharina E.; Mata, Ricardo A. ; Suhm, Martin A.
- Abstract
- The intramolecular OH···F hydrogen bond in 3,3,3-trifluoropropanol (TFP) exerts a subtle stabilizing effect that, when compared to the non-fluorinated analog, reorders the five distinguishable conformers and widens the gap between the two most stable structures. Here, we combine findings from Raman spectroscopy in supersonic expansions and high-level quantum-chemical calculations to bracket the energy difference between the two most stable TFP structures at 1.7(5) kJ mol(-1). The torsional potential energy surface suggests consecutive backbone and OH torsional motions for the conformer interconversion, which are discussed in the framework of supersonic jet cooling as a function of nozzle temperature. The picture of a bistable cold molecule with trans or gauche backbone emerges, in which the OH group controls the energy difference and modulates the high barrier separating the heavy atom frames.
- Issue Date
- 21-April-2015
- Journal
- Physical Chemistry, Chemical Physics
- Organization
- Institut für Physikalische Chemie
- ISSN
- 1463-9084
- eISSN
- 1463-9084
- Language
- English
- Sponsor
- German Research Foundation [DFG SU 121/2-2]