Rattling the cage: Micro- to mesoscopic structure in liquids as simple as argon and as complicated as water
Turton, D.A., Hunger, J., Stoppa, A., Thoman, A., Candelaresi, M., Hefter, G., Walther, M., Buchner, R. and Wynne, K. (2011) Rattling the cage: Micro- to mesoscopic structure in liquids as simple as argon and as complicated as water. Journal of Molecular Liquids, 159 (1). pp. 2-8.
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The water molecule has the convenient property that its molecular polarizability tensor is nearly isotropic while its dipole moment is large. As a result, the low-frequency anisotropic Raman spectrum of liquid water is mostly collision-induced and therefore reports primarily translational motions while the far-infrared (terahertz) and dielectric spectrum is dominated by rotational modes. Atomic and globular-molecular liquids have a zero dipole moment as well as an isotropic polarizability tensor. These spectrum-simplifying properties were exploited in a study of a number of liquids and solutions using ultrafast optical Kerr-effect (OKE) spectroscopy combined with dielectric relaxation spectroscopy (DRS), terahertz time-domain spectroscopy (THz-TDS), and terahertz field-induced second-harmonic generation (TFISH) spectroscopy. For room-temperature ionic liquids (RTILs), liquid water, aqueous salt solutions, noble gas liquids, and globular-molecular liquids it was found that, in each case, surprising structure and/or inhomogeneity is observed, ranging from mesoscopic clustering in RTILs to stretched-exponential dynamics in the noble gas liquids. For aqueous electrolyte solutions it is shown that the viscosity, normally described by the Jones-Dole expression, can be explained in terms of a jamming transition, a concept borrowed from soft condensed matter studies of glass transitions in colloidal suspensions.
|Publication Type:||Journal Article|
|Murdoch Affiliation:||School of Chemical and Mathematical Science|
|Copyright:||© 2010 Elsevier B.V.|
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