Bracketing subtle conformational energy differences between self-solvated and stretched trifluoropropanol.

Bracketing subtle conformational energy differences between self-solvated and stretched trifluoropropanol.
Heger, M.; Otto, K. E.; Mata, R. A.   & Suhm, M. A.  (2015) 
Physical Chemistry, Chemical Physics17(15) pp. 9899-9909.​

Authors
Heger, Matthias; Otto, Katharina E.; Mata, Ricardo A. ; Suhm, Martin A. 
Issue Date
21-April-2015
Type
Journal Article
Journal
Physical Chemistry, Chemical Physics 
Organization
Institut für Physikalische Chemie 
ISSN
1463-9084
eISSN
1463-9084
Language
English
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.
Publication of Göttingen University
Yes
Sponsor
Funder: German Research Foundation [DFG SU 121/2-2]
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