title: Bracketing subtle conformational energy differences between self-solvated and stretched trifluoropropanol.
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.
authors.affiliation: Institut für Physikalische Chemie, Universität Göttingen, Tammannstr. 6, 37077 Göttingen, Germany. msuhm@gwdg.de.
authors.forename: Matthias
authors.initials: M
authors.lastname: Heger
authors.forename: Katharina E
authors.initials: KE
authors.lastname: Otto
authors.forename: Ricardo A
authors.initials: RA
authors.lastname: Mata
authors.forename: Martin A
authors.initials: MA
authors.lastname: Suhm