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Article Dans Une Revue Journal of Physical Chemistry C Année : 2011

Hydrogen-Bond-Induced Supermolecular Assemblies in a Nanoconfined Tertiary Alcohol

Aziz Ghoufi
Ronan Lefort
Denis Morineau

Résumé

Tert-butanol is the molecular archetype of a variety of H-bonded systems that form micelle-like supermolecular clusters in the liquid state. This self-association process is characterized by a prepeak in the static structure factor. Recently, it has been shown by neutron scattering that this prepeak is totally suppressed in a nanoconfined geometry [Morineau, D.; Alba-Simionesco, C. J. Phys. Chem. Lett. 2010, 1, 7155.]. The authors have shown that excluded volume effects was one main ingredient of this suppression, but the question of the survival of H-bonded self-association in nanochannels has remained unresolved experimentally. From molecular dynamics simulations, we prove that self-association survives under confinement despite the absence of the prepeak. Furthermore, we show that its apparent suppression is due to a negative contribution arising from the liquid-porous solid correlations, which cannot be disentangled experimentally. Strikingly, the stability of micelle-like clusters surpasses the putative formation of interfacial H-bonds with surface silanols, leading to an unexpected hydrophobic interaction of tert-butanol with surface silica. This work highlights the foremost interest of combining neutron scattering and molecular simulations with a careful account of the complex situation encountered under confinement to better understand the molecular microstructure of H-bonded liquids.
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Dates et versions

hal-00713912 , version 1 (03-07-2012)

Identifiants

Citer

Aziz Ghoufi, Ivanne Hureau, Ronan Lefort, Denis Morineau. Hydrogen-Bond-Induced Supermolecular Assemblies in a Nanoconfined Tertiary Alcohol. Journal of Physical Chemistry C, 2011, 115 (36), pp.17761-17767. ⟨10.1021/jp205943p⟩. ⟨hal-00713912⟩
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