title: n-pentanol at high pressures: rotational isomerism in the liquid phase and the liquid-solid phase transition.
abstract: The vibrational spectrum of liquids constituted of chain molecules is difficult to analyze because it may have contributions of different rotational isomers. In turn, with a proper vibrational assignment, this feature allows us to extract information about the effect of temperature or pressure on the molecular conformations in the liquid state. In this regard, the information on the vibrational spectrum in the solid phase greatly simplifies the vibrational analysis of the different rotational conformers existing in the liquid, as the molecules usually present all-trans conformations in the crystalline state. Here we report room-temperature Raman experiments on n-pentanol performed in a sapphire-anvil cell up to 3 GPa. A detailed analysis of the liquid-solid phase transition occurring at 1.3 GPa is provided. The analysis of the Raman spectrum in the solid phase allows the identification of the bands due to the different rotational isomers present in the liquid. The analysis of the spectral region corresponding to skeletal vibrations of the carbon chain (800-1200 cm(-1)) indicates that gauche conformers are promoted by the application of pressure. The analysis of the intensity ratio of those bands assigned to trans and gauge conformations is used to calculate the change in molecular volume ascribed to the trans-gauge isomerization process. We find a value similar to that found in n-alkanes, i.e., -0.88 cm(3) mol(-1). In addition, we find indication that pressure varies the proportions of the different gauge conformers. Thus, it appears that the GTTt to TGTt transition in the carbon chain is favored at high pressures. As expected, a smaller change in the molecular volume accompanies this conformation change.
authors.affiliation: Departamento de Química Física I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain. vgbanoza@quim.ucm.es
authors.forename: V G
authors.initials: VG
authors.lastname: Baonza
authors.forename: M
authors.initials: M
authors.lastname: Taravillo
authors.forename: A
authors.initials: A
authors.lastname: Cazorla
authors.forename: S
authors.initials: S
authors.lastname: Casado
authors.forename: M
authors.initials: M
authors.lastname: Cáceres