2016
DOI: 10.1515/pac-2015-1201
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From solutions to molecular emulsions

Abstract: Concentration fluctuations play an important role in the statistical description of the stability of liquids, particularly in the neighborhood of phase transitions. Classical thermodynamics is blind to fluctuations, and statistical thermodynamics is required to fully understand quantities such as the isothermal compressibility or heat capacity, by linking them to fluctuations of appropriate statistical microscopic quantities and showing that they are response functions. This is illustrated by the seminal Kirkw… Show more

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Cited by 25 publications
(41 citation statements)
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“…1 is not the case below this concentration range any more. Canceling the different scattering contributions has already been observed in some theoretical studies of various alcohol-based systems [52,[99][100][101]. The results in Fig.…”
supporting
confidence: 61%
“…1 is not the case below this concentration range any more. Canceling the different scattering contributions has already been observed in some theoretical studies of various alcohol-based systems [52,[99][100][101]. The results in Fig.…”
supporting
confidence: 61%
“…This particular example shows very clearly how domain oscillations appear in conjunction with a growth of the pre-peaks in the structure factors witnessing domain-domain correlations. These features look very similar to those we have reported in several types of aqueous mixtures [30,31]. Similar results are equally obtained when 2 is kept fixed while varying κ 2 .…”
Section: Successful Model: the G-srlasupporting
confidence: 89%
“…The several cases we wish to model concern the type of micro-segregation found in aqueous mixtures. For example, aqueous mixtures of small amphiphile molecules such as alcohols, are known to produce micro-segregation [28,29,30], which induces large pre-peaks in atom-atom structure factors [30]. IET are generally unable to provide solutions for such mixtures (as in water-1propanol) [31], or when they can, the description of the structure is very poor (as in water-methanol) [7].…”
Section: Introductionmentioning
confidence: 99%
“…It is usually relates to fluctuations, which concern principally the k = 0 part of the structure factor, as far as the stability of the system is considered [34]. Our experience in studying realistic 3D associating liquids, such as water or alcohols, indicates that fluctuations at k = 0, in addition to being related to clustering [42], play little or no role in the global stability of the system. On the contrary, they enhance stable local heterogeneity [42].…”
Section: Discussionmentioning
confidence: 99%
“…Our experience in studying realistic 3D associating liquids, such as water or alcohols, indicates that fluctuations at k = 0, in addition to being related to clustering [42], play little or no role in the global stability of the system. On the contrary, they enhance stable local heterogeneity [42]. Therefore, since in the present case, simulations indicate that bilayer-like clustering appears in the lower part of the phase diagram, they support the fact that this system is governed by charge ordering induced clustering everywhere in the phase diagram, albeit to various degrees.…”
Section: Discussionmentioning
confidence: 99%