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 and a liquid-liquid critical point. 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 give 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.Comment: 29 pages, 15 figure

Reflections: Academia's Emerging Crisis of Relevance and the Consequent Role of the Engaged Scholar

Universities are facing a crisis of relevance. While there are multiple reasons for this to be happening, one that deserves particular attention is the extent to which academic scholars do not see it as their role to engage in public and political discourse. However, increased engagement is unavoidable in an emerging educational context where the caliber of public discourse has become so degraded and social media is changing the nature of science and scientific discourse within society. Further, there is a demographic shift in play, where young scholars are seeking more impact from their work than their more senior colleagues. In this article, I begin the process of articulating what we know and what we don’t know about the evolving role of the engaged scholar by breaking the conversation into two parts. First, why should academic scholars engage in public and political discourse? Second, how can we structure a set of ground rules that could form what might be considered a handbook for public engagement? In the end, this article is about a reexamination of how we practice our craft, to what purpose and to which audiences.http://deepblue.lib.umich.edu/bitstream/2027.42/136168/1/1343_Hoffman.pd

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 3 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 {\bf 409}, 692 (2001)] that, even with no evidences 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 3-parameter space of the soft-core potential and we 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.Comment: 15 pages, 21 figure

Ab initio van der Waals interactions in simulations of water alter structure from mainly tetrahedral to high-density-like

The structure of liquid water at ambient conditions is studied in ab initio molecular dynamics simulations using van der Waals (vdW) density-functional theory, i.e. using the new exchange-correlation functionals optPBE-vdW and vdW-DF2. Inclusion of the more isotropic vdW interactions counteracts highly directional hydrogen-bonds, which are enhanced by standard functionals. This brings about a softening of the microscopic structure of water, as seen from the broadening of angular distribution functions and, in particular, from the much lower and broader first peak in the oxygen-oxygen pair-correlation function (PCF), indicating loss of structure in the outer solvation shells. In combination with softer non-local correlation terms, as in the new parameterization of vdW-DF, inclusion of vdW interactions is shown to shift the balance of resulting structures from open tetrahedral to more close-packed. The resulting O-O PCF shows some resemblance with experiment for high-density water (A. K. Soper and M. A. Ricci, Phys. Rev. Lett., 84:2881, 2000), but not directly with experiment for ambient water. However, an O-O PCF consisting of a linear combination of 70% from vdW-DF2 and 30% from experiment on low-density liquid water reproduces near-quantitatively the experimental O-O PCF for ambient water, indicating consistency with a two-liquid model with fluctuations between high- and low-density regions

Public perceptions of shale gas in the UK : framing effects and decision heuristics

Using two equivalent descriptions of the shale gas development process, we asked individuals to indicate their levels of support as well as their perceptions of the risks and costs involved. In version 1, shale gas development was framed as ‘fracking’, whereas under version 2 it was framed as ‘using hydraulic pressure to extract natural gas from the ground’. We find that individuals’ support for shale gas development is much lower when using the term ‘fracking’ as opposed to the synonymous descriptive term, and moreover, these differences were substantive. Our analysis suggests that these differences appear to be largely the result of different assessments of the risks associated with ‘fracking’ as opposed to ‘using hydraulic pressure to extract natural gas from the ground’. Our proposed explanation for these differences rests on the idea that shale gas development is a technical and complex process and many individuals will be bounded by the rationality of scientific knowledge when it comes to understanding this process. In turn, individuals may be relying on simple decision heuristics shaped by the way this issue is framed by the media and other interested parties which may constrain meaningful discourse on this topic with the public. Our findings also highlight some of the potential pitfalls when it comes to relying on survey research for assessing the public’s views towards complex environmental issues