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  • Title: Hydrophobic Hydration in Water-tert-Butyl Alcohol Solutions by Extended Depolarized Light Scattering.
    Author: Comez L, Paolantoni M, Lupi L, Sassi P, Corezzi S, Morresi A, Fioretto D.
    Journal: J Phys Chem B; 2015 Jul 23; 119(29):9236-43. PubMed ID: 25436859.
    Abstract:
    Molecular dynamics and structural properties of water-tert-butyl alcohol (TBA) mixtures are studied as a function of concentration by extended depolarized light scattering (EDLS) experiments. The wide frequency range, going from fraction to several thousand GHz, explored by EDLS allows distinguishing TBA rotational dynamics from structural relaxation of water and intermolecular vibrational and librational modes of the solution. Contributions to the water relaxation originating from two distinct populations, i.e. hydration and bulk water, are clearly identified. The dynamic retardation factor of hydration water with respect to the bulk, ξ ≈ 4, almost concentration independent, is one of the smallest found by EDLS among a variety of systems of different nature and complexity. This result, together with the small number of water molecules perturbed by the presence of TBA, supports the idea that hydrophobic simple molecules are less effective than hydrophilic and more complex molecules in perturbing the H-bond network of liquid water. At increasing TBA concentrations the average number of perturbed water molecules shows a pronounced decrease and the characteristic frequency of librational motions reduces significantly, both of which are results consistent with the occurrence of self-aggregation of TBA molecules.
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