Liquid-liquid phase transition for an attractive isotropic potential with wide repulsive range

We investigate how the phase diagram of a repulsive soft-core attractive potential, with a liquid-liquid phase transition in addition to the standard gas-liquid phase transition, changes by varying the parameters of the potential. We extend our previous work on short soft-core ranges to the case of large soft-core ranges, by using an integral equation approach in the hypernetted-chain approximation. We show, using a modified van der Waals equation we recently introduced, that if there is a balance between the attractive and repulsive part of the potential this potential has two fluid-fluid critical points well separated in temperature and in density. This implies that for the repulsive (attractive) energy U R ( U A ) and the repulsive (attractive) range w R ( w A ) the relation U R ∕ U A ∝ w R ∕ w A holds for short soft-core ranges, while U R ∕ U A ∝ 3 w R ∕ w A holds for large soft-core ranges

Homogeneous Crystal Nucleation Near a Metastable Fluid-Fluid Phase Transition

Several scenarios exist for the protein crystallization and aggregation in solutions near a metastable fluid-fluid phase separation below the solubility line. Based on computations, it was proposed that the fluid-fluid critical point enhances the crystallization rate by many orders of magnitude, while, based on experiments, it was proposed that the fluid-fluid spinodal controls the crystallization rate. Using molecular dynamic simulations for an isotropic model with sticky interaction, we show that neither of these scenarios adequately describes the crystallization mechanism near a metastable fluid-fluid phase separation. We find that the emergence of the high-density fluid inside the spinodal drastically enhances the crystal nucleation in the subcritical region following Ostwald's rule of stages

Optimization of crystal nucleation close to a metastable fluid-fluid phase transition

The presence of a metastable fluid-fluid critical point is thought to dramatically influence the crystallization pathway, increasing the nucleation rate by many orders of magnitude over the predictions of classical nucleation theory. We use molecular dynamics simulations to study the kinetics of crystallization in the vicinity of this metastable critical point and throughout the metastable fluid-fluid phase diagram. To quantitatively understand how the fluid-fluid phase separation affects the crystal nucleation, we evaluate accurately the kinetics and reconstruct the thermodynamic free-energy landscape of crystal formation. Contrary to expectations, we find no special advantage of the proximity of the metastable critical point on the crystallization rates. However, we find that the ultrafast formation of a dense liquid phase causes the crystallization to accelerate both near the metastable critical point and almost everywhere below the fluid-fluid spinodal line. These results unveil three different scenarios for crystallization that could guide the optimization of the process in experiments

Finite-size scaling investigation of the liquid-liquid critical point in ST2 water and its stability with respect to crystallization.

The liquid-liquid critical point scenario of water hypothesizes the existence of two metastable liq- uid phases low-density liquid (LDL) and high-density liquid (HDL) deep within the supercooled region. The hypothesis originates from computer simulations of the ST2 water model, but the stabil- ity of the LDL phase with respect to the crystal is still being debated. We simulate supercooled ST2 water at constant pressure, constant temperature, and constant number of molecules N for N ≤ 729 and times up to 1 μs. We observe clear differences between the two liquids, both structural and dynamical. Using several methods, including finite-size scaling, we confirm the presence of a liquid-liquid phase transition ending in a critical point. We find that the LDL is stable with respect to the crystal in 98% of our runs (we perform 372 runs for LDL or LDL-like states), and in 100% of our runs for the two largest system sizes (N = 512 and 729, for which we perform 136 runs for LDL or LDL-like states). In all these runs, tiny crystallites grow and then melt within 1 μs. Only for N ≤ 343 we observe six events (over 236 runs for LDL or LDL-like states) of spontaneous crystal- lization after crystallites reach an estimated critical size of about 70 ± 10 molecules

Confinement of Anomalous Liquids in Nanoporous Matrices

Using molecular dynamics simulations, we investigate the effects of different nanoconfinements on complex liquids-e.g., colloids or protein solutions-with density anomalies and a liquid-liquid phase transition (LLPT). In all the confinements, we find a strong depletion effect with a large increase in liquid density near the confining surface. If the nano confinement is modeled by an ordered matrix of nanoparticles (NPs), we find that the anomalies are preserved. On the contrary, if the confinement is modeled by a disordered matrix of NPs, we find a drastically different phase diagram: the LLPT shifts to lower pressures and temperatures, and the anomalies become weaker, as the disorder increases. We find that the density heterogeneities induced by the disordered matrix are responsible for the weakening of the LLPT and the disappearance of the anomalies

Molecular dynamics study of orientational cooperativity in water

Recent experiments on liquid water show collective dipole orientation fluctuations dramatically slower than expected (with relaxation time >tation, the self-dipole randomization time tr, which is an upper limit on ta; we find that tr5ta. Third, to check if there are correlated domains of dipoles in water which have large relaxation times compared to the individual dipoles, we calculate the randomization time tbox of the site-dipole field, the net dipole moment formed by a set of molecules belonging to a box of edge Lbox. We find that the site-dipole randomization time tbox2.5ta for Lbox3 , i.e., it is shorter than the same quantity calculated for the self-dipole. Finally, we find that the orientational correlation length is short even at low T

Liquid-liquid phase transition for an attractive isotropic potential with wide repulsive range

We investigate how the phase diagram of a repulsive soft-core attractive potential, with a liquid-liquid phase transition in addition to the standard gas-liquid phase transition, changes by varying the parameters of the potential. We extend our previous work on short soft-core ranges to the case of large soft-core ranges, by using an integral equation approach in the hypernetted-chain approximation. We show, using a modified van der Waals equation we recently introduced, that if there is a balance between the attractive and repulsive part of the potential this potential has two fluid-fluid critical points well separated in temperature and in density. This implies that for the repulsive (attractive) energy U R ( U A ) and the repulsive (attractive) range w R ( w A ) the relation U R ∕ U A ∝ w R ∕ w A holds for short soft-core ranges, while U R ∕ U A ∝ 3 w R ∕ w A holds for large soft-core ranges

Liquid-liquid phase transition for soft-core attractive potential

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

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

Nanoscale Dynamics of Phase Flipping in Water near its Hypothesized Liquid-Liquid Critical Point

One hypothesized explanation for water's anomalies imagines the existence of a liquid-liquid (LL) phase transition line separating two liquid phases and terminating at a LL critical point. We simulate the classic ST2 model of water for times up to 1000 ns and system size up to N 5 729. We find that for state points near the LL transition line, the entire system flips rapidly between liquid states of high and low density. Our finite-size scaling analysis accurately locates both the LL transition line and its associated LL critical point. We test the stability of the two liquids with respect to the crystal and find that of the 350 systems simulated, only 3 of them crystallize and these 3 for the relatively small system size N5343 while for all other simulations the incipient crystallites vanish on a time scales smaller than < 100 ns