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Article Dans Une Revue Physical Chemistry Chemical Physics Année : 2021

Isomeric effects in structure formation and dielectric dynamics of different octanols

Jennifer Bolle
  • Fonction : Auteur
Peter Bierwirth
  • Fonction : Auteur
Martina Pozar
  • Fonction : Auteur
Michael Paulus
  • Fonction : Auteur
Philipp Münzner
  • Fonction : Auteur
Christian Albers
Susanne Dogan
  • Fonction : Auteur
Mirko Elbers
  • Fonction : Auteur
Göran Surmeier
  • Fonction : Auteur
Roland Böhmer
  • Fonction : Auteur
Metin Tolan
  • Fonction : Auteur
Christian Sternemann
  • Fonction : Auteur
  • PersonId : 1113353

Résumé

The understanding of the microstructure of associated liquids promoted by hydrogen-bonding and constrained by steric hindrance is highly relevant in chemistry physics, biology and for many aspects of daily life. In this study we use a combination of X-ray diffraction, dielectric spectroscopy and molecular dynamics simulations to reveal temperature induced changes in the microstructure of different octanol isomers, i.e., linear 1-octanol and branched 2-, 3- and 4-octanol. In all octanols, the hydroxyl groups form the bases of chain-, cyclic- or loop-like bonded structures that are separated by outwardly directed alkyl chains. This clustering is analyzed through the scattering pre-peaks observed from X-ray scattering and simulations. The charge ordering which pilots OH aggregation can be linked to the strength of the Debye process observed in dielectric spectroscopy. Interestingly, all methods used here converge to the same interpretation: as one moves from 1-octanol to the branched octanols, the cluster structure evolves from loose large aggregates to a larger number of smaller, tighter aggregates. All alcohols exhibit a peculiar temperature dependence of both the pre-peak and Debye process, which can be understood as a change in microstructure promoted by chain association with increased chain length possibly assisted by ring-opening effects. All these results tend to support the intuitive picture of the entropic constraint provided by branching through the alkyl tails and highlight its capital entropic role in supramolecular assembly.

Domaines

Matériaux
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Dates et versions

hal-03377138 , version 1 (14-10-2021)

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Jennifer Bolle, Peter Bierwirth, Martina Pozar, Aurélien Perera, Michael Paulus, et al.. Isomeric effects in structure formation and dielectric dynamics of different octanols. Physical Chemistry Chemical Physics, 2021, ⟨10.1039/d1cp02468j⟩. ⟨hal-03377138⟩
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