Ice Ih anomalies: Thermal contraction, anomalous volume isotope effect, and pressure-induced amorphization
Ice Ih displays several anomalous thermodynamic properties such as thermal contraction at low temperatures, an anomalous volume isotope effect (VIE) rendering the volume of D2O ice greater than that of H2O ice, and a pressure-induced transition to the high-density amorphous (HDA) phase. Furthermore, the anomalous VIE increases with temperature, despite its quantum-mechanical origin. Here, embedded-fragment ab initio second-order many-body perturbation (MP2) theory in the quasiharmonic approximation (QHA) is applied to the Gibbs energy of an infinite, proton-disordered crystal of ice Ih at wide ranges of temperatures and pressures. The quantum effect of nuclei moving in anharmonic potentials is taken into account from first principles without any empirical or nonsystematic approximation to either the electronic or vibrational Hamiltonian. MP2 predicts quantitatively correctly the thermal contraction at low temperatures, which is confirmed to originate from the volume-contracting hydrogen-bond bending modes (acoustic phonons). It qualitatively reproduces (but underestimates) the thermal expansion at higher temperatures, caused by the volume-expanding hydrogen-bond stretching (and to a lesser extent librational) modes. The anomalous VIE is found to be the result of subtle cancellations among closely competing isotope effects on volume from all modes. Consequently, even ab initio MP2 with the aug-cc-pVDZ and aug-cc-pVTZ basis sets has difficulty reproducing this anomaly, yielding qualitatively varied predictions of the sign of the VIE depending on such computational details as the choice of the embedding field. However, the temperature growth of the anomalous VIE is reproduced robustly and is ascribed to the librational modes. These solid-state MP2 calculations, as well as MP2 Born–Oppenheimer molecular dynamics, find a volume collapse and a loss of symmetry and long-range order in ice Ih upon pressure loading of 2.35 GPa or higher. Concomitantly, rapid softening of acoustic phonons is observed starting around 2 GPa. They constitute a computational detection of a mechanical instability in ice Ih and the resulting pressure-induced amorphization to HDA.
When solutes are small compared to the size of the ions in an ionic liquid, energetic heterogeneities associated with charge enhanced (stiff) and charge depleted (soft) nanoenvironments are sampled. In a recent article [J. C. Araque et al., J. Phys. Chem. B 119(23), 7015-7029 (2015)], we explored large deviations from Stokes-Einstein translational diffusion caused by such a heterogeneity. The current article is set to explore the effect of soft and stiff solvent environments (i.e., structure) on OH-bond rotations in the case of water and small alcohols in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (Im1,2+NTf2−). Is solute rotational dynamics heterogeneous? If so, are solute rotations and translations coupled in the sense that stiff and soft solvent environments hinder or speed up both types of dynamics? For the systems studied here, there appears to be a clear connection between translations, rotations, and stiff/soft solvent environments. We also discuss interesting asymmetries of the correlation between solutes with anions and cations.
USA Today: On 19 May, during a presentation to award the National Medals of Science and Technology, President Obama announced that he was establishing a campaign for children to submit ideas about the future of science, discovery, and exploration in the US. The White House has set up a page on its website with a form for idea submissions. The campaign was prompted at the White House Science Fair in April, when nine-year-old Jacob Leggette asked Obama if he had any advisers who were kids.
Science News: Last year astronomers observed a burst of light—tagged ASASSN-15lh—from 3 billion light-years away that they reported as the brightest supernova ever seen. With a peak luminosity of around 550 billion times that of the Sun, the supernova was twice as bright as the previous record holder. Now Peter Brown of Texas A&M University in College Station and his colleagues say that ASASSN-15lh might not be a supernova. About 80 days after ASASSN-15lh peaked in brightness and began fading away, Brown's team saw it get brighter again. After another 80 days, the object was emitting as much UV light as some supernovae. An increase in brightness of supernova remnants can be caused by various known mechanisms, but none of the spectral absorption lines characteristic of those explanations have been found. Instead, Brown's team suggests that ASASSN-15lh is actually a star being swallowed by the supermassive black hole at the center of the source galaxy. The flash was emitted from near the galaxy's center, and the increase in brightness could stem from a second piece of the star falling into the black hole.
The present paper focuses on the numerical simulation of the interaction of laser-generated bubbles with a free surface, including comparison of the results with instances from high-speed videos of the experiment. The Volume Of Fluid method was employed for tracking liquid and gas phases while compressibility effects were introduced with appropriate equations of state for each phase. Initial conditions of the bubble pressure were estimated through the traditional Rayleigh Plesset equation. The simulated bubble expands in a non-spherically symmetric way due to the interference of the free surface, obtaining an oval shape at the maximum size. During collapse, a jet with mushroom cap is formed at the axis of symmetry with the same direction as the gravity vector, which splits the initial bubble to an agglomeration of toroidal structures. Overall, the simulation results are in agreement with the experimental images, both quantitatively and qualitatively, while pressure waves are predicted both during the expansion and the collapse of the bubble. Minor discrepancies in the jet velocity and collapse rate are found and are attributed to the thermodynamic closure of the gas inside the bubble.
Self-propelled, chemically powered colloidal locomotors are swimmers designed to transverse small scale landscapes in a range of applications involving micropumping, sensing, and cargo transport. Although applications can require precise navigation and onboard steering mechanisms, here we examine by calculation how locomotors through their hydrodynamic interaction can navigate along a boundary. We adopt an engine model consisting of a spherical Janus colloid coated with a symmetrical catalyst cap, which converts fuel into a product solute. The solute is repelled from the colloid through a repulsive interaction, which occurs over a distance much smaller than the swimmer radius. Within this thin interaction layer, a concentration difference develops along the surface, which generates a pressure gradient as pressure balances the interaction force of the solute with the surface. The pressure gradient drives a slip flow towards the high concentration, which propels the particle oppositely, away from product accumulation (self-diffusiophoresis). To study boundary guidance, the motion near an infinite no-slip planar wall that does not adsorb solute is obtained by analytical solution of the solute conservation and the Stokes equations using bispherical coordinates. Several regimes of boundary interaction unfold: When the colloid is oriented with its cap axisymmetrically facing the wall, it is repelled by the accumulation of solute in the gap between the swimmer and the wall. With the cap opposite to the wall, the swimmer moves towards the wall by the repulsion from the solute accumulating on the cap side, but very large caps accumulate solute in the gap, and the motor stops. For oblique approach with the cap opposite to the wall and small cap sizes, the swimmer is driven to the wall by accumulation on the cap side, but rotates as it approaches the wall, and eventually scatters as the cap reorients and faces the wall. For a swimmer approaching obliquely with a larger cap (again facing away from the wall), boundary navigation results as the accumulation of product in the gap suppresses rotation and provides a normal force, which directs the swimmer to skim along the surface at a fixed distance and orientation or to become stationary. We also demonstrate how gravity can force transitions between skimming and stationary states.
Radiation reaction (RR) force plays an important role in gamma ray production in the interaction of ultraintense laser with relativistic counterpropagating electron at intensity 1022 W/cm2 and beyond. The relationship between emission spectrum and initial kinetic energy of electron at such intensities is yet to be clear experimentally. On the other hand, the energy from both the relativistic electron beam and laser pulse may be converted into the gamma rays. Therefore, the conversion efficiency of energy purely from laser pulse into gamma rays is of great interest. We present simulation results of an electron dynamics in strong laser field by taking into account the RR effects. We investigated how the RR effects influence the emission spectrum and photon number distribution for different laser condition. We showed that the peaks of emission spectra are suppressed if higher initial kinetic energy of electron interacts with long laser pulse duration. We then list the conversion efficiencies of laser pulse energy into gamma ray. We note that an electron with energy of 40 MeV would convert up to 80% of the total of electromagnetic work and initial kinetic energy of electron when interacting with 10 fs laser pulse at intensity 2×1023 W/cm2. For a bunch of electron with charge 1 nC would emit around 0.1 J of energy into gamma ray emission.
Collective synchronous motion of the phases is introduced in a model for the stochastic passive advection-diffusion of a scalar with external forcing. The model for the phase coupling dynamics follows the well known Kuramoto model paradigm of limit-cycle oscillators. The natural frequencies in the Kuramoto model are assumed to obey a given scale dependence through a dispersion relation of the drift-wave form −βk1+k2, where β is a constant representing the typical strength of the gradient. The present aim is to study the importance of collective phase dynamics on the characteristic time evolution of the fluctuation energy and the formation of coherent structures. Our results show that the assumption of a fully stochastic phase state of turbulence is more relevant for high values of β, where we find that the energy spectrum follows a k−7/2 scaling. Whereas for lower β there is a significant difference between a-synchronised and synchronised phase states, one could expect the formation of coherent modulations in the latter case.
The near vacuum campaign on the National Ignition Facility has concentrated its efforts over the last year on finding the optimum target geometry to drive a symmetric implosion at high convergence ratio (30×). As the hohlraum walls are not tamped with gas, the hohlraum is filling with gold plasma and the challenge resides in depositing enough energy in the hohlraum before it fills up. Hohlraum filling is believed to cause symmetry swings late in the pulse that are detrimental to the symmetry of the hot spot at high convergence. This paper describes a series of experiments carried out to examine the effect of increasing the distance between the hohlraum wall and the capsule (case to capsule ratio) on the symmetry of the hot spot. These experiments have shown that smaller Case to Capsule Ratio (CCR of 2.87 and 3.1) resulted in oblate implosions that could not be tuned round. Larger CCR (3.4) led to a prolate implosion at convergence 30× implying that inner beam propagation at large CCR is not impeded by the expanding hohlraum plasma. A Case to Capsule ratio of 3.4 is a promising geometry to design a round implosion but in a smaller hohlraum where the hohlraum losses are lower, enabling a wider cone fraction range to adjust symmetry.
The impact of sheared toroidal rotation on the evolution of pressure driven magnetic islands in tokamak plasmas is investigated using a resistive magnetohydrodynamics model augmented by a neoclassical Ohm's law. Particular attention is paid to the asymptotic matching data as the Mercier indices are altered in the presence of sheared flow. Analysis of the nonlinear island Grad-Shafranov equation shows that sheared flows tend to amplify the stabilizing pressure/curvature contribution to pressure driven islands in toroidal tokamaks relative to the island bootstrap current contribution. As such, sheared toroidal rotation tends to reduce saturated magnetic island widths.