Local structure of liquid carbon controls diamond nucleation

Diamonds melt at temperatures above 4000 K. There are no measurements of the steady-state rate of the reverse process: diamond nucleation from the melt, because experiments are difficult at these extreme temperatures and pressures. Using numerical simulations, we estimate the diamond nucleation rate and find that it increases by many orders of magnitude when the pressure is increased at constant supersaturation. The reason is that an increase in pressure changes the local coordination of carbon atoms from three-fold to four-fold. It turns out to be much easier to nucleate diamond in a four-fold coordinated liquid than in a liquid with three-fold coordination, because in the latter case the free-energy cost to create a diamond-liquid interface is higher. We speculate that this mechanism for nucleation control is relevant for crystallization in many network-forming liquids. On the basis of our calculations, we conclude that homogeneous diamond nucleation is likely in carbon-rich stars and unlikely in gaseous planets

Phase behavior and structure of model colloid-polymer mixtures confined between two parallel planar walls

Using Gibbs ensemble Monte Carlo simulations and density functional theory we investigate the fluid-fluid demixing transition in inhomogeneous colloid-polymer mixtures confined between two parallel plates with separation distances between one and ten colloid diameters covering the complete range from quasi two-dimensional to bulk-like behavior. We use the Asakura-Oosawa-Vrij model in which colloid-colloid and colloid-polymer interactions are hard-sphere like, whilst the pair potential between polymers vanishes. Two different types of confinement induced by a pair of parallel walls are considered, namely either through two hard walls or through two semi-permeable walls that repel colloids but allow polymers to freely penetrate. For hard (semi-permeable) walls we find that the capillary binodal is shifted towards higher (lower) polymer fugacities and lower (higher) colloid fugacities as compared to the bulk binodal; this implies capillary condensation (evaporation) of the colloidal liquid phase in the slit. A macroscopic treatment is provided by a novel symmetric Kelvin equation for general binary mixtures, based on the proximity in chemical potentials of statepoints at capillary coexistence and the reference bulk coexistence. Results for capillary binodals compare well with those obtained from the classic version of the Kelvin equation due to Evans and Marini Bettolo Marconi [J. Chem. Phys. 86, 7138 (1987)], and are quantitatively accurate away from the fluid-fluid critical point, even at small wall separations. For hard walls the density profiles of polymers and colloids inside the slit display oscillations due to packing effects for all statepoints. For semi-permeable walls either similar structuring or flat profiles are found, depending on the statepoint considered.Comment: 15 pages, 13 figure

Diffraction based Hanbury Brown and Twiss interferometry performed at a hard x-ray free-electron laser

We demonstrate experimentally Hanbury Brown and Twiss (HBT) interferometry at a hard X-ray Free Electron Laser (XFEL) on a sample diffraction patterns. This is different from the traditional approach when HBT interferometry requires direct beam measurements in absence of the sample. HBT analysis was carried out on the Bragg peaks from the colloidal crystals measured at Linac Coherent Light Source (LCLS). We observed high degree (80%) spatial coherence of the full beam and the pulse duration of the monochromatized beam on the order of 11 fs that is significantly shorter than expected from the electron bunch measurements.Comment: 32 pages, 10 figures, 2 table

Remote participation during glycosylation reactions of galactose building blocks: Direct evidence from cryogenic vibrational spectroscopy

The stereoselective formation of 1,2‐cis‐glycosidic bonds is challenging. However, 1,2‐cis‐selectivity can be induced by remote participation of C4 or C6 ester groups. Reactions involving remote participation are believed to proceed via a key ionic intermediate, the glycosyl cation. Although mechanistic pathways were postulated many years ago, the structure of the reaction intermediates remained elusive owing to their short‐lived nature. Herein, we unravel the structure of glycosyl cations involved in remote participation reactions via cryogenic vibrational spectroscopy and first principles theory. Acetyl groups at C4 ensure α‐selective galactosylations by forming a covalent bond to the anomeric carbon in dioxolenium‐type ions. Unexpectedly, also benzyl ether protecting groups can engage in remote participation and promote the stereoselective formation of 1,2‐cis‐glycosidic bonds

Effects of hole-doping on the magnetic ground state and excitations in the edge-sharing CuO2_2 chains of Ca2+x_{2+x}Y2−x_{2-x}Cu5_5O10_{10}

Neutron scattering experiments were performed on the undoped and hole-doped Ca$_{2+x}$Y$_{2-x}$Cu$_5$O$_{10}$, which consists of ferromagnetic edge-sharing CuO$_2$ chains. It was previously reported that in the undoped Ca$_2$Y$_2$Cu$_5$O$_{10}$ there is an anomalous broadening of spin-wave excitations along the chain, which is caused mainly by the antiferromagnetic interchain interactions [Matsuda $et$ $al.$, Phys. Rev. B 63, 180403(R) (2001)]. A systematic study of temperature and hole concentration dependencies of the magnetic excitations shows that the magnetic excitations are softened and broadened with increasing temperature or doping holes irrespective of $Q$ direction. The broadening is larger at higher $Q$. A characteristic feature is that hole-doping is much more effective to broaden the excitations along the chain. It is also suggested that the intrachain interaction does not change so much with increasing temperature or doping although the anisotropic interaction and the interchain interaction are reduced. In the spin-glass phase ($x$=1.5) and nearly disordered phase ($x$=1.67) the magnetic excitations are much broadened in energy and $Q$. It is suggested that the spin-glass phase originates from the antiferromagnetic clusters, which are caused by the hole disproportionation.Comment: 8 pages, submitted to Phys. Rev.

The development of a questionnaire on metacognition for students in higher education

Background Interest in the role of metacognition has been steadily rising in most forms of education. This study focuses on the construction of a questionnaire for measuring metacognitive knowledge, metacognitive regulation and metacognitive responsiveness among students in higher education and the subsequent process of testing to determine its validity. Purpose The aim of the study was to construct an original instrument for measuring features of metacognition, henceforth referred to as the Awareness of Independent Learning Inventory (AILI), and further to establish the similarities and differences between this model and existing instruments for measuring metacognition. Sample The AILI questionnaire was distributed to 1058 students in various types of Teacher Training Institutes in the Netherlands and Belgium. The abridged English version of the questionnaire was administered to another sample of 729 students reading Economics and Business Administration at the University of Maastricht in the south of the Netherlands. Design and methods The AILI instrument was constructed on the basis of a facet design along two dimensions: components of metacognition and topics of concern to students in higher education. The data gathered with the instrument was analyzed by means of a generalisability study and a decision study, respectively. The validity of the instrument was investigated by using confirmatory factor analysis. Results The generalisability study showed that the reliability of the instrument was satisfactory. The decision study revealed that the number of items included in the questionnaire could be reduced substantially by leaving out two components of one of the dimensions in the facet design, without losing too much generalisability. The validity study showed that there was a considerable level of congruity between parts of the AILI questionnaire and the relevant parts of the Motivated Strategies for Learning Questionnaire (MSLQ). Conclusions The AILI questionnaire is a reliable and valid instrument for measuring metacognitive knowledge, regulation and responsiveness. It is suitable for use in the evaluation of the effects of interventions that purport to increase metacognitive knowledge, regulation and responsiveness of students in higher education

Complete Solving for Explicit Evaluation of Gauss Sums in the Index 2 Case

Let $p$ be a prime number, $q=p^f$ for some positive integer $f$, $N$ be a positive integer such that $\gcd(N,p)=1$, and let \k be a primitive multiplicative character of order $N$ over finite field \fq. This paper studies the problem of explicit evaluation of Gauss sums in "\textsl{index 2 case}" (i.e. f=\f{\p(N)}{2}=[\zn:\pp], where \p(\cd) is Euler function). Firstly, the classification of the Gauss sums in index 2 case is presented. Then, the explicit evaluation of Gauss sums G(\k^\la) (1\laN-1) in index 2 case with order $N$ being general even integer (i.e. N=2^{r}\cd N_0 where $r,N_0$ are positive integers and $N_03$ is odd.) is obtained. Thus, the problem of explicit evaluation of Gauss sums in index 2 case is completely solved

Electrical current distribution across a metal-insulator-metal structure during bistable switching

Combining scanning electron microscopy (SEM) and electron-beam-induced current (EBIC) imaging with transport measurements, it is shown that the current flowing across a two-terminal oxide-based capacitor-like structure is preferentially confined in areas localized at defects. As the thin-film device switches between two different resistance states, the distribution and intensity of the current paths, appearing as bright spots, change. This implies that switching and memory effects are mainly determined by the conducting properties along such paths. A model based on the storage and release of charge carriers within the insulator seems adequate to explain the observed memory effect.Comment: 8 pages, 7 figures, submitted to J. Appl. Phy