Advances in wide bandgap SiC for optoelectronics

Silicon carbide (SiC) has played a key role in power electronics thanks to its unique physical properties like wide bandgap, high breakdown field, etc. During the past decade, SiC is also becoming more and more active in optoelectronics thanks to the progress in materials growth and nanofabrication. This paper will review the advances in fluorescent SiC for white light-emitting diodes, covering the poly-crystalline doped SiC source material growth, single crystalline epitaxy growth of fluorescent SiC, and nanofabrication of SiC to enhance the extraction efficiency for fluorescent SiC based white LEDs.     

Equatorial contra axial polar substituents. The relation of a chemical reaction to stereochemical substituent constants

The established rates of glycoside hydrolysis reactions were analyzed using free energy relationship plots based on substituent constants that depend on whether the substituent is axial or equatorial. In all cases good correlations were found when assuming either that the transition state had a charged ring-oxygen atom or that it had a charged anomeric carbon atom. The spontaneous hydrolysis of 2,4-dinitrophenyl beta-glycopyranosides and the acidic hydrolysis of methyl beta-D-glycopyranosides were found to give a good correlation, when 100% charge at the ring-oxygen in the transition state of these reactions is assumed. The acidic hydrolysis of methyl alpha-glycopyranosides was found to give good correlations regardless of whether 100% charge at the ring-oxygen or 100% charge at the anomeric carbon was assumed. The findings clearly demonstrate how crucial the stereochemistry of even remote polar substituents is for their electronic effect on chemical reaction.     

Lattice dynamics of solid xenon under pressure

We use density-functional perturbation theory to obtain the phonon spectrum of fcc xenon under pressure. Thermodynamic properties obtained within the quasiharmonic approximation are in fair to good agreement with experiment at zero pressure. The transition pressure from the fcc to hcp phase is predicted to occur at 5 GPa. The fcc structure is found to be dynamically stable up to a pressure of 100 GPa, beyond which the phonon modes at the X and L symmetry points soften. We attribute the observed sluggish kinetics of the fcc-hcp transition to the small energy difference between the phases as well as to the high dynamical stability of the fcc phase.     

Quantum origin of the oxygen storage capability of ceria

The microscopic mechanism behind the extraordinary ability of ceria to store, release, and transport oxygen is explained on the basis of first-principles quantum mechanical simulations. The oxygen-vacancy formation energy in ceria is calculated for different local environments. The reversible CeO2-Ce2O3 reduction transition associated with oxygen-vacancy formation and migration is shown to be directly coupled with the quantum process of electron localization.     

Exclusive measurement of the pp --> pppi(+)pi(-) reaction near threshold

The pp-->pp pi(+) pi(-) reaction has been measured exclusively near threshold at CELSIUS. The total cross sections are nearly an order of magnitude lower than expected from previous inclusive measurements. The differential cross sections reveal pp-->pp(*)(1440)-->pp sigma = pp(pi(+)pi(-))(I = l = 0) as the dominant process as well as significant contributions from p(*)-->Delta(++)pi(-)-->psigma. The observed anisotropy in the proton angular dependence is consistent with heavy-meson exchange. In the invariant mass spectra, no narrow structures of statistical relevance (3sigma) are found.     

Compound Poisson Approximation of the Number of Exceedances in Gaussian Sequences

Consider a finite sequence of Gaussian random variables. Count the number of exceedances of some level a, i.e. the number of values exceeding the level. Let this level and the length of the sequence increase simultaneously so that the expected number of exceedances remains fixed. It is well-known that if the long-range dependence is not too strong, the number of exceeding points converges in distribution to a Poisson distribution. However, for sequences with some individual large correlations, the Poisson convergence is slow due to clumping. Using Steins method we show that, at least for m-dependent sequences, the rate of convergence is improved by using compound Poisson as approximating distribution. An explicit bound for the convergence rate is derived for the compound Poisson approximation, and also for a subclass of the compound Poisson distribution, where only clumps of size two are considered. Results from numerical calculations and simulations are also presented.     

On the distribution of the length of the longest increasing subsequence of random permutations

The authors consider the length, , of the longest increasing subsequence of a random permutation of numbers. The main result in this paper is a proof that the distribution function for , suitably centered and scaled, converges to the Tracy-Widom distribution of the largest eigenvalue of a random GUE matrix. The authors also prove convergence of moments. The proof is based on the steepest descent method for Riemann-Hilbert problems, introduced by Deift and Zhou in 1993 in the context of integrable systems. The applicability of the Riemann-Hilbert technique depends, in turn, on the determinantal formula of Gessel for the Poissonization of the distribution function of .

     

Thiol–ene coupling reaction of fatty acid monomers

The reactivities and reaction rates of the thiol–ene coupling reaction of 2‐ethyl‐(hydroxymethyl)‐1,3‐propanediol trimercapto acetate and 2‐ethyl‐(hydroxymethyl)‐1,3‐propanediol trimercapto propionate with two common unsaturated fatty acid methyl esters (methyl oleate and methyl linoleate) were evaluated. The reactions were monitored with real‐time IR and ¹H NMR, which both showed that the mercapto acetate was more reactive than the mercapto propionate. Both thiols were more prone to add to the monounsaturated methyl oleate than to methyl linoleate, which contained two unconjugated double bonds. According to bond energy calculations, the thiol hydrogen of mercapto acetate was somewhat more difficult to abstract than the hydrogen of mercapto propionate. Consequently, the formed S? C bond in the acetate case was stronger than in the propionate case, and so the equilibrium was more shifted toward the addition products. The real‐time IR measurements also showed that the cis unsaturation in methyl oleate isomerized much more quickly than that in methyl linoleate, and this also had an impact on the overall addition rate of the thiols because a trans unsaturation was more reactive than a cis unsaturation. The higher isomerization rates in the oleate systems, compared with those of the linoleate systems, was suggested to be due to a more restricted rotation along the C? C bond of the reacted unsaturation in linoleate. This study showed the importance of trans unsaturations in obtaining reasonable reaction rates in thiol–ene reactions with fatty acid derivatives. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6346–6352, 2004     

Core-level binding energy shifts in dilute alloys

Core level binding energy shifts for the element A of a large number of dilute alloys AB have been measured, where the concentration of the dilute component A is 10% or less. The experimental shifts are analysed in terms of alloy heat of formation data, for which we have used Miedema's semi-empirical scheme. Good overall agreement is obtained between the experimental data and the calculated values, encouraging the use of electron spectroscopy for evaluating solution energies of metallic systems.