No Arabic abstract
According to extensive experimental findings, the Ginzburg temperature $t_{G}$ for ionic fluids differs substantially from that of nonionic fluids [Schroer W., Weig{a}rtner H. 2004 {it Pure Appl. Chem.} {bf 76} 19]. A theoretical investigation of this outcome is proposed here by a mean field analysis of the interplay of short and long range interactions on the value of $t_{G}$. We consider a quite general continuous charge-asymmetric model made of charged hard spheres with additional short-range interactions (without electrostatic interactions the model belongs to the same universality class as the 3D Ising model). The effective Landau-Ginzburg Hamiltonian of the full system near its gas-liquid critical point is derived from which the Ginzburg temperature is calculated as a function of the ionicity. The results obtained in this way for $t_{G}$ are in good qualitative and sufficient quantitative agreement with available experimental data.
We find that a system of particles interacting through a simple isotropic potential with a softened core is able to exhibit a rich phase behavior including: a liquid-liquid phase transition in the supercooled phase, as has been suggested for water; a gas-liquid-liquid triple point; a freezing line with anomalous reentrant behavior. The essential ingredient leading to these features resides in that the potential investigated gives origin to two effective core radii.
We consider fluids where the attractive interaction at distances slightly larger than the particle size is dominated at larger distances by a repulsive contribution. A previous investigation of the effects of the competition between attraction and repulsion on the liquid-vapour transition and on the correlations is extended to the study of the stability of liquid-vapour phase separation with respect to freezing. We find that this long-range repulsive part of the interaction expands the region where the fluid-solid transition preempts the liquid-vapour one, so that the critical point becomes metastable at longer attraction ranges than those required for purely attractive potentials. Moreover, the large density fluctuations that occur near the liquid-vapour critical point are greatly enhanced by the competition between attractive and repulsive forces, and encompass a much wider region than in the attractive case. The decay of correlations for states where the compressibility is large is governed by two characteristic lengths, and the usual Ornstein-Zernike picture breaks down except for the very neighborhood of the critical point, where one length reduces to the commonly adopted correlation length, while the other one saturates at a finite value.
A model of polar fluid is studied theoretically. The interaction potential, in addition to dipole-dipole term, possesses a dispersion contribution of the van der Waals-London form. It is found that when the dispersion force is comparable to dipole-dipole interaction, the fluid separates into coexisting liquid and gas phases. The calculated critical parameters are in excellent agreement with Monte Carlo simulations. When the strength of dispersion attraction is bellow critical, no phase separation is found.
The high frequency dynamics of fluid oxygen have been investigated by Inelastic X-ray Scattering. In spite of the markedly supercritical conditions ($Tapprox 2 T_c$, $P>10^2 P_c$), the sound velocity exceeds the hydrodynamic value of about 20%, a feature which is the fingerprint of liquid-like dynamics. The comparison of the present results with literature data obtained in several fluids allow us to identify the extrapolation of the liquid vapor-coexistence line in the ($P/P_c$, $T/T_c$) plane as the relevant edge between liquid- and gas-like dynamics. More interestingly, this extrapolation is very close to the non metal-metal transition in hot dense fluids, at pressure and temperature values as obtained by shock wave experiments. This result points to the existence of a connection between structural modifications and transport properties in dense fluids.
Three one-body profiles that correspond to local fluctuations in energy, in entropy, and in particle number are used to describe the equilibrium properties of inhomogeneous classical many-body systems. Local fluctuations are obtained from thermodynamic differentiation of the density profile or equivalently from average microscopic covariances. The fluctuation profiles follow from functional generators and they satisfy Ornstein-Zernike relations. Computer simulations reveal markedly different fluctuations in confined fluids with Lennard-Jones, hard sphere, and Gaussian core interactions.