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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 86 (1987), S. 1521-1532 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A phenomenological theory of the liquid wetting layer is presented. Its predictions are compared to those of earlier simpler models as well as to recent experimental results. Special attention is given to the critical region and to the crossover from the complete wetting regime to the critical wetting regime.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 7591-7602 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We investigate the structural and thermodynamic properties of the isotropic phase of the hard ellipse liquid for several length-to-breadth ratios (2,4,6), using the hypernetted chain (HNC) and Percus–Yevick (PY) integral equation theories. A comparison with the recent simulations of Cuesta and Frenkel [Phys. Rev. A 42, 2126 (1990)] is made. Satisfactory agreement is found with PY theory for small aspect ratios, while for larger ones, HNC results become superior. In addition, HNC (but not PY) predicts the orientational instability of the isotropic phase at a finite density for systems of aspect ratios 4 and 6, in good agreement with computer simulation results. In order to investigate the order of the orientational phase transition, density functional theories (DFT) calculations are carried out using as input the direct correlation functions of the isotropic liquid obtained in this work. No first-order transition is found within the version of DFT used herein.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 594-602 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We use the consistent set of hypernetted chain (HNC) equations to investigate the stability of liquid and vapor phases of simple fluids. We calculate the phase diagram and discuss the physical (spinodal) and mathematical (termination line) singularities of the theory. The latter delimits a region where the HNC equations have no physically acceptable solutions. Additionally, we confirm that the physical solutions of the HNC equation correspond to local minima of the consistent grand potential which, however, appears to be unbounded from below.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 110 (1999), S. 10058-10066 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Criticality in a fluid of dielectric constant D that exhibits Ising-type behavior is studied as additional electrostatic (i.e., ionic) interactions are turned on. An exploratory perturbative calculation is performed for small ionicity as measured by the ratio of the electrostatic energy e2/Da (of two univalent charges, ±e, separated by the atomic/ionic diameter a) to kBTc0 which represents the strength of the short-range nonionic (i.e., van der Waals) interactions in the uncharged fluid. With the aid of distinct transformations for the short-range and for the Coulombic interactions, an effective Hamiltonian with coefficients depending on the ionicity is derived at the Debye-Hückel limiting-law level for a fully symmetric model. The crossover between classical (mean-field) and Ising behavior is then estimated using a Ginzburg criterion. This indicates that the reduced crossover temperature depends only weakly on the ionicity (and on the range of the nonionic potentials); however, the trends do correlate with the, much stronger, dependence observed experimentally. © 1999 American Institute of Physics.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 105 (1996), S. 2875-2883 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Recent experiments revealed a striking scaling behavior of the low and ultralow interfacial tension of microemulsions. A description of this behavior based on the Helfrich elastic free energy, which is symmetric in the principal curvatures c1 and c2, appears to be inconsistent. We show that, within the phenomenological theory of membrane bending elasticity, symmetry breaking between the two principal curvatures seems to be required in order to explain the low, but nonzero, values of the interfacial tension and its temperature dependence. We propose two simple generalizations of the Helfrich free energy which describe the experimental results. The first considers a quadratic elastic free energy and anisotropy in the membrane which breaks the symmetry between the two principal curvatures. In the second, which is applicable to systems with positive saddle-splay rigidities, the symmetry between the two principal curvatures is spontaneously broken by inclusion of higher-order terms in the curvatures in order to stabilize the free energy of the system. This analysis provides a straightforward method to obtain estimates of the bending elastic constants from interfacial tension measurements. Experiments confirming the theoretical picture are presented and values for κ and κ¯, for a variety of systems, are obtained. © 1996 American Institute of Physics.
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 108 (1998), S. 4189-4198 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We have calculated the structure and the interfacial tension of microemulsions on the phase inversion path, using a single-order parameter Landau theory. We show that the observed scaling behavior of the interfacial tensions [T. Sottmann and R. Strey, J. Chem. Phys. 106, 8606 (1997)] is described by a simple theoretical model based on the assumption that the ratio of the length scales characterizing microemulsions is a universal function of the reduced temperature, on the phase inversion path. This assumption is based on the results of small angle neutron scattering experiments on this series of systems, at the optimal microemulsion temperature [T. Sottman, R. Strey, and S.-H. Chen, J. Chem. Phys. 106, 6483 (1997)] and on the scaling properties of the Landau free energy on the phase inversion path. © 1998 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 89 (1985), S. 1514-1519 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 93 (1989), S. 4132-4138 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 1534-1538 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: An extended version of the hypernetted chain equation is presented. It allows for fluid inhomogeneity and for three-body interactions. Consistent expressions for thermodynamic functions are given. It is argued that thermodynamic consistency holds even though statistical mechanical relationships are not obeyed. Singularities in the hypernetted chain equation, related to loss of convexity of the associated free energy functional, prevent a complete description of liquid/vapor coexistence in a Lennard-Jones fluid.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 85 (1986), S. 490-499 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We have studied the interfacial properties of droplets of (cutoff and shifted) Lennard-Jones fluids in the canonical ensemble, using mean field theory. We have examined the effects of system size, overall density (supersaturation) and temperature on the density profiles, density and pressure at the center of the droplet, and surface tension. The numerical accuracy of the theory was tested by extensive comparisons of the results with the molecular dynamics simulations of Thompson et al. Good agreement was found. We have used the theory to calculate the energy of formation of a droplet and the stability temperature Ts for droplet formation as a function of the system size and overall density. We find Ts to be lower than the coexistence temperature for the planar surface, and to fall as the drop size falls.
    Type of Medium: Electronic Resource
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