Liquid-liquid transition and critical point in sulfur.

The liquid-liquid transition (LLT), in which a single-component liquid transforms into another one via a first-order phase transition, is an intriguing phenomenon that has changed our perception of the liquid state. LLTs have been predicted from computer simulations of water1,2, silicon3, carbon dioxide4, carbon5, hydrogen6 and nitrogen7. Experimental evidence has been found mostly in supercooled (that is, metastable) liquids such as Y2O3-Al2O3 mixtures8, water9 and other molecular liquids10-12. However, the LLT in supercooled liquids often occurs simultaneously with crystallization, making it difficult to separate the two phenomena13. A liquid-liquid critical point (LLCP), similar to the gas-liquid critical point, has been predicted at the end of the LLT line that separates the low- and high-density liquids in some cases, but has not yet been experimentally observed for any materials. This putative LLCP has been invoked to explain the thermodynamic anomalies of water1. Here we report combined in situ density, X-ray diffraction and Raman scattering measurements that provide direct evidence for a first-order LLT and an LLCP in sulfur. The transformation manifests itself as a sharp density jump between the low- and high-density liquids and by distinct features in the pair distribution function. We observe a non-monotonic variation of the density jump with increasing temperature: it first increases and then decreases when moving away from the critical point. This behaviour is linked to the competing effects of density and entropy in driving the transition. The existence of a first-order LLT and a critical point in sulfur could provide insight into the anomalous behaviour of important liquids such as water.

Anisotropic thermal expansion of black phosphorus from nanoscale dynamics of phosphorene layers.

Black phosphorus (bP) is a crystalline material which can be seen as an ordered stacking of two-dimensional layers, referred to as phosphorene. The knowledge of the linear thermal expansion coefficients (LTECs) of bP is of great interest in the field of 2D materials for a better understanding of the anisotropic thermal properties and exfoliation mechanism of this material. Despite several theoretical and experimental studies, important uncertainties remain in the determination of the LTECs of bP. Here, we report accurate thermal expansion measurements along the three crystallographic axes using in situ high temperature X-ray diffraction. From the progressive reduction of the diffracted intensities with temperature, we monitored the loss of the crystal structure of bP across the investigated temperature range, evidencing two thermal expansion regimes at temperature below and above 706 K. Below 706 K, a strong out-of-plane anisotropy can be observed, while at temperatures above 706 K a larger thermal expansion occurs along the a crystallographic direction. From our data and by taking advantage of ab initio optimization, we propose a detailed anisotropic thermal expansion mechanism of bP, which leads to an inter- and intra-layer destabilization. An interpretation of it, based on the high T perturbation of the stabilizing sp orbital mixing effect, is provided, consistent with the high pressure data.

Electrical conductivity during incipient melting in the oceanic low-velocity zone.

The low-viscosity layer in the upper mantle, the asthenosphere, is a requirement for plate tectonics. The seismic low velocities and the high electrical conductivities of the asthenosphere are attributed either to subsolidus, water-related defects in olivine minerals or to a few volume per cent of partial melt, but these two interpretations have two shortcomings. First, the amount of water stored in olivine is not expected to be higher than 50 parts per million owing to partitioning with other mantle phases (including pargasite amphibole at moderate temperatures) and partial melting at high temperatures. Second, elevated melt volume fractions are impeded by the temperatures prevailing in the asthenosphere, which are too low, and by the melt mobility, which is high and can lead to gravitational segregation. Here we determine the electrical conductivity of carbon-dioxide-rich and water-rich melts, typically produced at the onset of mantle melting. Electrical conductivity increases modestly with moderate amounts of water and carbon dioxide, but it increases drastically once the carbon dioxide content exceeds six weight per cent in the melt. Incipient melts, long-expected to prevail in the asthenosphere, can therefore produce high electrical conductivities there. Taking into account variable degrees of depletion of the mantle in water and carbon dioxide, and their effect on the petrology of incipient melting, we calculated conductivity profiles across the asthenosphere for various tectonic plate ages. Several electrical discontinuities are predicted and match geophysical observations in a consistent petrological and geochemical framework. In moderately aged plates (more than five million years old), incipient melts probably trigger both the seismic low velocities and the high electrical conductivities in the upper part of the asthenosphere, whereas in young plates, where seamount volcanism occurs, a higher degree of melting is expected.