Biomedical subjects

G Malescio

Publications and source records attributed to G Malescio.

17 recordsLinked to original sources

PubMed2006

Universality in the phase behavior of soft matter: a law of corresponding states.

We show that the phase diagram of substances whose molecular structure changes upon varying the thermodynamic parameters can be mapped, through state-dependent scaling, onto the phase diagram of systems of molecules having fixed structure. This makes it possible to identify broad universality classes in the complex phase scenario exhibited by soft matter, and enlightens a surprisingly close connection between puzzling phase phenomena and familiar behaviors. The analysis presented provides a straightforward way for deriving the phase diagram of soft substances from that of simpler reference systems. This method is applied here to study the phase behavior exhibited by two significative examples of soft matter with temperature-dependent molecular structure: thermally responsive colloids and polymeric systems. A region of inverse melting, i.e., melting upon isobaric cooling, is predicted at relatively low pressure and temperature in polymeric systems.

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PubMed2004

Liquid-liquid phase transitions for soft-core attractive potentials.

Using event-driven molecular dynamics simulations, we study a three-dimensional one-component system of spherical particles interacting via a discontinuous potential combining a repulsive square soft core and an attractive square well. In the case of a narrow attractive well, it has been shown that this potential has two metastable gas-liquid critical points. Here we systematically investigate how the changes of the parameters of this potential affect the phase diagram of the system. We find a broad range of potential parameters for which the system has both a gas-liquid critical point C1 and a liquid-liquid critical point C2. For the liquid-gas critical point we find that the derivatives of the critical temperature and pressure, with respect to the parameters of the potential, have the same signs: they are positive for increasing width of the attractive well and negative for increasing width and repulsive energy of the soft core. This result resembles the behavior of the liquid-gas critical point for standard liquids. In contrast, for the liquid-liquid critical point the critical pressure decreases as the critical temperature increases. As a consequence, the liquid-liquid critical point exists at positive pressures only in a finite range of parameters. We present a modified van der Waals equation which qualitatively reproduces the behavior of both critical points within some range of parameters, and gives us insight on the mechanisms ruling the dependence of the two critical points on the potential's parameters. The soft-core potential studied here resembles model potentials used for colloids, proteins, and potentials that have been related to liquid metals, raising an interesting possibility that a liquid-liquid phase transition may be present in some systems where it has not yet been observed.

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PubMed2002

Metastable liquid-liquid phase transition in a single-component system with only one crystal phase and no density anomaly.

We investigate the phase behavior of a single-component system in three dimensions with spherically-symmetric, pairwise-additive, soft-core interactions with an attractive well at a long distance, a repulsive soft-core shoulder at an intermediate distance, and a hard-core repulsion at a short distance, similar to potentials used to describe liquid systems such as colloids, protein solutions, or liquid metals. We showed [Nature (London) 409, 692 (2001)] that, even with no evidence of the density anomaly, the phase diagram has two first-order fluid-fluid phase transitions, one ending in a gas-low-density-liquid (LDL) critical point, and the other in a gas-high-density-liquid (HDL) critical point, with a LDL-HDL phase transition at low temperatures. Here we use integral equation calculations to explore the three-parameter space of the soft-core potential and perform molecular dynamics simulations in the interesting region of parameters. For the equilibrium phase diagram, we analyze the structure of the crystal phase and find that, within the considered range of densities, the structure is independent of the density. Then, we analyze in detail the fluid metastable phases and, by explicit thermodynamic calculation in the supercooled phase, we show the absence of the density anomaly. We suggest that this absence is related to the presence of only one stable crystal structure.

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PubMed2001

Generic mechanism for generating a liquid-liquid phase transition.

Recent experimental results indicate that phosphorus--a single-component system--can have a high-density liquid (HDL) and a low-density liquid (LDL) phase. A first-order transition between two liquids of different densities is consistent with experimental data for a variety of materials, including single-component systems such as water, silica and carbon. Molecular dynamics simulations of very specific models for supercooled water, liquid carbon and supercooled silica predict a LDL-HDL critical point, but a coherent and general interpretation of the LDL-HDL transition is lacking. Here we show that the presence of a LDL and a HDL can be directly related to an interaction potential with an attractive part and two characteristic short-range repulsive distances. This kind of interaction is common to other single-component materials in the liquid state (in particular, liquid metals), and such potentials are often used to describe systems that exhibit a density anomaly. However, our results show that the LDL and HDL phases can occur in systems with no density anomaly. Our results therefore present an experimental challenge to uncover a liquid-liquid transition in systems like liquid metals, regardless of the presence of a density anomaly.

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PubMed2001

Simple fluids with complex phase behavior.

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 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 the presence of two effective radii in the repulsive core. The potential investigated appears appropriate for a class of spherical polymeric micelles recently investigated.

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PubMed2000

Structural stability of simple classical fluids: universal properties of the lyapunov-exponent measure

A threshold for the stability of the solution of integral equations for the pair correlation function of a classical fluid can be determined from the Floquet matrix for the iterative form of the integral equation. Correspondingly, a measure of the structural stability of the fluid, analogous to the Lindemann ratio for a solid, is provided by the Lyapunov exponent lambda that is related to the perturbed dynamics. The behavior of lambda as a function of density, temperature, interatomic potential, and closure relations for the integral equation, is analyzed and discussed. In analogy with the Lindemann parameter, we find-for the hypernetted-chain-type closures-that lambda(T/T(inst)) is "quasiuniversal," i.e., very weakly dependent on the interaction potential, up to a temperature T/T(inst) approximately 5, where T(inst) is the stability-threshold temperature. We show how this result connects the Lyapunov exponent measure of the pair structure with the equation of state of the fluid.

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PubMed2000

Structural stability of simple fluids and accuracy of integral-equation theories

The ability to describe the structural stability of a fluid may represent a stringent test for the overall physical soundness of an integral-equation theory. The accuracy of some approximate closures of the Ornstein-Zernike equation is discussed in relation to the estimates of the density threshold of structural stability of the fluid that are obtained through an analysis of the iterative form of the integral equation. The connection with the random-close-packing threshold of hard spheres is also investigated.

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PubMed1996