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Generalized van der Waals theory of liquid-liquid phase transitions.pdf

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Generalized van der Waals theory of liquid-liquid phase transitions

a r X i v : c o n d - m a t / 0 5 1 2 6 4 0 v 1 [ c o n d - m a t .s t a t - m e c h ] 2 4 D e c 2 0 0 5 Generalized van der Waals theory of liquid-liquid phase transitions Yu. D. Fomin, V. N. Ryzhov, and E. E. Tareyeva Institute for High Pressure Physics, Russian Academy of Sciences, Troitsk 142190, Moscow Region, Russia (Dated: February 6, 2008) In the framework of the thermodynamic perturbation theory for fluids we study how the phase diagram of an isotropic repulsive soft-core attractive potential, where a liquid-liquid phase transition exists in addition to the standard gas-liquid phase transition, changes by varying the parameters of the potential. We show that existence of the liquid-liquid transition is determined by the interplay of the parameters of the potential and the structure of a reference liquid. PACS numbers: 61.20.Gy, 61.20.Ne, 61.20.Mv, 64.60.Kw Despite the growing interest to the possible polymor- phic phase transitions in liquids and glasses [1, 2] the nature of different phases which can be found in dense (and possibly metastable) liquids is still puzzling. The coexistence of different phases, while common for mix- tures, is unexpected for a simple fluid. In principle, the rules of thermodynamics do not forbid the existence of more than two different fluid phases in a simple fluid, however, from a common experience only two of them are well known: a low density fluid (vapor) and a high density fluid (liquid) phases. At the same time in recent years experimental evidences of such features of phase diagram as liqiud-liquid transitions, polyamorphism, etc appeared for a wide range of systems including water, Si, I, Se, S, P , etc [1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11]. The complexity of the phase diagrams in these substances may be a result of complex interactions depending on the intermolecular orientations. At the same time exploring the possibility that simple fluids interacting through isotropic potentials may ex- hibit the similar behav