# Applications of the Stell-Hemmer Potential to Understanding Second Critical Points in Real Systems

## Abstract

We consider the novel properties of the Stell-Hemmer core-softened potentials. First we explore how the theoretically predicted second critical point for these potentials is related to the occurrence of the experimentally observed solid-solid isostructural critical point. We then discuss how this class of potentials can generate anomalies analogous to those found experimentally in liquid water.

PACS numbers: 61.20.Gy, 61.25.Em, 65.70.+y, 64.70.Ja

Simple liquids are often modeled by pairwise potentials possessing a repulsive core, mimicking the impenetrability of atoms or molecules, and an attractive part, responsible for the gas-liquid transition. For a fluid in which the interaction potential $`\varphi (r)`$ has a hard core plus an attractive part, a “softened” hard core (Fig. 1) can produce an additional line of phase transition . A general argument by Stell and Hemmer based on the symmetry between occupied and unoccupied cells in lattice gas models of fluids predicts that the the additional line of phase transition can end at a novel critical point . An explicit example of the occurrence of a second line of first order transition is given in  for a one-dimensional continuum model of a fluid with long-range attraction ; this first order line can end in a critical point depending on the details of the core-softened potential. The general result is that if the repulsive part (core) of the interaction potential has a concave part (which makes it “core-softened”), then it is likely that such a novel transition occurs . Stell and Hemmer  relate the occurrence of a high-density, low-temperature critical point to the known isostructural solid-solid critical point observed in some experiments .

To understand the occurrence of a second transition, consider the Gibbs potential at zero temperature. The shape of the energy $`U`$ as a function of the volume $`V`$ should have the same “core-softened” shape (i.e. possesses a region where it is concave) as the inter particle potential. The stable phase is then determined by the Gibbs potential

$$G(P,T)\underset{V}{\text{min}}\{U+PVTS\},$$
(1)   
where $`S`$ is the entropy. The right hand side of (1) is shown in Fig. 2 as a function of $`V`$, for $`T=0`$ and for different values of pressure $`P`$. At low $`P`$, the stable phase of the system has a specific volume at which the average inter-particle distance is near to the minimum of the inter-particle potential. The concavity in $`U`$ assures that, on increasing $`P`$, an additional minimum appears in $`U+PVTS`$. For high enough $`P`$, this minimum will become the lowest one and the stable phase of the system will be the one for which the mean inter-particle distance is “inside” the softened part of the core.

For one-dimensional models, a first-order transition at $`T=0`$ between a dense and an open phase occurs at a pressure that can be determined exactly with the graphical construction of Fig. 2 .

For short-range interactions, the entropy gives a huge contribution in one dimension, making any phase transition disappear for $`T>0`$. Hence, the contribution of the entropic term $`TS`$ makes the double well structure of Fig. 2 disappear when $`T>0`$. This may not be true in higher dimensions, and so a line of first order transitions (eventually ending in a critical point) could be present for $`T>0`$.

Stronger evidence for the occurrence of a high-density, low-temperature critical point is given in  upon developing and refining analytic methods to investigate the high-density region of the phase diagram of a fluid. The methods used are in principle for a dense fluid, and hence would predict a liquid-liquid transition. However, the second critical point can be related to the isostructural critical point occurring in the solid phase of materials such as Cs,Ce and of mixtures such as Sm-S and Ce-Th . For all these materials the shape of the effective pair potential is “core-softened” .

Many liquid metals (Ga and Sn are prominent examples) have static structure factors $`𝒮(k)`$ that show weak subsidiary maxima, or asymmetries, in the main peak of $`𝒮(k)`$ that suggest the presence of a “structured” core that is not infinitely steep. First-principle calculation of the effective ion-ion potential for Ga leads to a core-softened potential . Monte Carlo simulations with this potential reproduce for Ga the observed anomalies in $`𝒮(k)`$. Inversion of the experimental structure factors for In, Zn, Al, Ge, Sn, Cs, Rb, Tl, and Pb, using random phase approximation or the Ornstein-Zernike equation with a closure, also results in effective core-softened potentials (Fig. 3.

In addition to the second critical point, core-softened potentials can produce a density anomaly, i.e. the material can expand upon cooling. The occurrence of crossing isotherms was observed in the model . It was noted that, although isotherms crossing is not a common feature in fluids, it is to be found whenever $`(V/T)_P`$ changes sign, as it does in water at approximately 4C and atmospheric pressure. Using thermodynamic arguments, Debenedetti et al. also noted that a “softened core” can cause the thermal expansion coefficient $`\alpha _P(1/V)(V/T)_P`$ to be negative .

One-dimensional fluids  with core-softened potentials have been studied in relation to the molecular origin of the negative thermal expansion in two fluids, water and tellurium , which have an effective core-softened potential .

Conversely, various lines of reasoning led to the introduction of phenomenological potentials for water that are core-softened . The inversion of the oxygen-oxygen radial distribution function $`g_{oo}(r)`$ for water gives an effective potential $`\varphi `$ (Fig. 3) that is core-softened . Thus core-softened potentials can be considered as zeroth-order models for water.

It is natural to expect that a core-softened potential can induce a density anomaly. In a liquid, the typical inter-particle distance is distributed inside the attractive part of the potential. As temperature decreases, the distribution peaks around the minimum of the potential, causing the system to expand (Fig. 4).

In addition to the density anomaly, further studies  of core-softened one-dimensional fluids have discovered anomalies in the isothermal compressibility and specific heat response functions in water. These anomalies are related to the existence of a critical point at $`T=0`$ and high density, similar to what is conjectured to occur in real water .

The region where the liquid has a density anomaly must have an upper boundary in the P-T plane; this boundary defines the line of density maxima ($`T_{\text{Md}}`$). The occurrence of this boundary can be understood by first recalling that

$$\alpha _P\delta V\delta S\left(P\delta V^2+\delta V\delta E\right).$$
(2)   
When $`\alpha _P`$ is negative, the term $`\delta V\delta E`$ must also be negative; the fluctuations that give a negative sign to $`\delta V\delta E`$ correspond to the regions of the fluid where particles penetrate the softened part of the core. However, the $`\alpha _P`$ anomaly must vanish at high enough pressures where the positive $`P\delta V^2`$ term dominates.

Core-softened potentials with no attractive part and no liquid-gas transition were studied in 2 and 3 dimensions by Young and Alder, giving a P-T phase diagram with a solid-fluid coexistence line similar to Ce or Cs . The fluid-solid coexistence line has a negatively sloped region, as in water. The phase diagram for a core-softened potential in 2d with no attractive part has been studied by Jagla , who explicitly finds a density anomaly in the fluid region. These results indicate that the softened part of the core can be solely responsible for the density anomaly and suggest that it can be related to the existence of negatively-sloped melting lines.

The slope of a melting line is related through the Clausius-Clapeyron equation $`dP/dT=\mathrm{\Delta }S/\mathrm{\Delta }V`$ to the difference $`\mathrm{\Delta }S`$ in the entropies and $`\mathrm{\Delta }V`$ in the volumes between the fluid and the solid. On the other hand, the sign of the coefficient of thermal expansion $`\alpha _P\delta S\delta V`$ depends on the cross-correlation between entropy and volume fluctuations. Near a melting line, one expects the relevant fluctuations in a liquid to be “solid-like” as they trigger the nucleation process leading to the first order liquid-solid transition (Fig. 5). This means that the sign of $`\alpha _P\delta V\delta S`$ will be likely the same as $`dP/dT=\mathrm{\Delta }S/\mathrm{\Delta }V`$.

Extensive studies of core-softened potentials in two dimensions via molecular dynamics simulations  reveal a phase diagram (Fig. 6) similar to that of water (Fig. 7. Near the negatively-sloped part of the liquid-solid freezing line ($`\mathrm{\Delta }S/\mathrm{\Delta }V<0`$), the liquid exhibits a density anomaly ($`\alpha _P\delta S\delta V<0`$). In agreement with the thermodynamic considerations of , the model also reproduces the existence of a region where the isothermal compressibility grows anomalously upon cooling in the same way as in water. Moreover, the model succeeds in reproducing anomalies not only in the statics, but also in the dynamics: there is a region in which the diffusion constant anomalously increases with pressure  as in water. The locus of points where the diffusivity has a maximum upon varying pressure defines the pressure of maximum diffusivity line ($`P_{\text{MD}}`$), which has been observed in water, in core-softened models, and in SPC-E simulated water ; in all these cases the $`P_{\text{MD}}`$ line occurs at higher pressures than the $`T_{\text{Md}}`$ line. The joint occurrence of density and diffusivity anomalies is also observed in two-dimensional simulations of the Gaussian-core model  that, although not possessing a hard core, has a concave region in the repulsive part of the potential.

Theories relating diffusivity to entropic contributions  would predict the occurrence of an anomaly in the diffusion $`(D/P)_T>0`$ to be related to an anomaly in the entropy $`(P/P)_T>0`$. On the other hand, whenever there is a density anomaly, an entropy anomaly occurs, as the entropy reaches a maximum along isotherms on the $`T_{\text{Md}}`$ line. This is a consequence of the Maxwell relation $`(S/P)_T=(V/T)_P`$.

In conclusion, core-softened potentials are simple realistic potentials that can model complex fluid behavior. In addition to the well-known liquid-gas transition, an analysis of the shape of free energies at low temperatures reveals the presence of a second transition, which can either be interpreted as a solid-solid or a liquid-liquid transition. Simulations indicate that if a liquid-liquid critical point exists it is likely to be in the region of the phase diagram where the liquid is metastable, at least for core-softened potentials in two dimensions . The presence of a liquid-liquid critical point provides one explanation of how anomalies in the response functions for core-softened potentials could occur—although other scenarios are also possible . Although core-softened potentials are capable of exhibiting most of the anomalies present in liquid water, most materials that are known to have an effective core-softened potential have not been studied as extensively as water, and thus the presence of anomalies in them is still an open question. Moreover, the relationship between anomalies of static (e.g., entropy) and dynamic (e.g., diffusivity) quantities is still an open issue that can be explored using core-softened potentials, possibly within the framework of existing theories .

We thank M. Canpolat, E. La Nave, M. Meyer, S. Sastry, F. Sciortino, A. Skibinsky R. J. Speedy, F. W. Starr, G. S. Stell and D. Wolf, for enlighting discussions, and NSF for support.

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