X‐ray excited optical luminescence from crystalline silicon

Synchrotron based X‐ray excited optical luminescence (XEOL) has been measured with many direct bandgap semiconductors. We present XEOL measurements on crystalline silicon (Si), obtained despite of its indirect bandgap and the consequently low luminescence efficiency. Spectra of monocrystalline and multicrystalline (mc) Si at room temperature are compared to theoretical spectra. A possible application in the synchrotron‐based research on mc‐Si is exemplified by combining XEOL, X‐ray fluorescence (XRF) spectroscopy, photoluminescence (PL) spectroscopy, and microscope images of grain boundaries. This approach can be utilized to investigate the recombination activity of metal precipitates, to analyze areas of different lifetimes on mc‐Si samples and to correlate additional material parameters to XRF measurements. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nonlinear ultrasonic waves in bubbly liquids with nonhomogeneous bubble distribution: Numerical experiments

This paper deals with the nonlinear propagation of ultrasonic waves in mixtures of air bubbles in water, but for which the bubble distribution is nonhomogeneous. The problem is modelled by means of a set of differential equations which describes the coupling of the acoustic field and bubbles vibration, and solved in the time domain via the use and adaptation of the SNOW-BL code. The attenuation and nonlinear effects are assumed to be due to the bubbles exclusively. The nonhomogeneity of the bubble distribution is introduced by the presence of bubble layers (or clouds) which can act as acoustic screens, and alters the behaviour of the ultrasonic waves. The effect of the spatial distribution of bubbles on the nonlinearity of the acoustic field is analyzed. Depending on the bubble density, dimension, shape, and position of the layers, its effects on the acoustic field change. Effects such as shielding and resonance of the bubbly layers are especially studied. The numerical experiments are carried out in two configurations: linear and nonlinear, i.e. for low and high excitation pressure amplitude, respectively, and the features of the phenomenon are compared. The parameters of the medium are chosen such as to reproduce air bubbly water involved in the stable cavitation process.     

On enhanced tuning capabilities of external cavity lasers using acousto-optic modulators

For an enhanced tuning of an external-cavity Littrow diode laser at 670 nm a new approach based on the frequency controlling of intra-cavity acousto-optic modulators (AOM) has been developed and tested. Using a method called “mode shaking” a nearly continuously laser tuning over a frequency range of 186 GHz (0.279 nm) within a time interval of 20 ms has been achieved. A further method called “far laser frequency jump” allows frequency changes of up to 1080 GHz (1.6 nm) between two spectral regions of the diode laser emission range within about 50 μs.     

Aza‐Diels–Alder reaction between cyclopentadiene and protonated N‐phenylethyliminoacetates of 8‐phenylmenthol and 8‐phenylneomenthol: a density functional theory study

The cycloaddition between glyoxylate imines possessing two chiral auxiliaries, N‐(R)‐ or N‐(S)‐1‐phenylethyl and 8‐phenylmenthyl or 8‐phenylneomenthyl, and cyclopentadiene is described. Computational calculations using density functional theory with the Becke, three‐parameter, Lee–Yang–Parr functional and the 6‐31G(d) basis set were performed to better understand the highly diastereoselective mechanism and the exo‐selectivity observed experimentally for these ionic aza‐Diels–Alder reactions. Copyright © 2011 John Wiley & Sons, Ltd.     

A theoretical study of hemiacetal formation from the reaction of methanol with derivatives of CX3CHO (X = H,F, Cl,Br and I)

A theoretical study of the hemiacetal formation reaction between methanol and CX₃CHO (X = H, F, Cl, Br, and I) has been carried out using density functional theory and Becke, three‐parameter, Lee–Yang–Parr/6‐311++G(d,p) computational methods. The stationary points of the reaction between the isolated molecules and the reaction catalyzed by an additional methanol molecule have been characterized. Because the final products present a stereogenic center, the potential autocatalysis of the reaction has been examined and also the possibility of spontaneous generation of chirality when the hemiacetal molecules are involved in the transition state structure. High barriers are found in the reaction between the isolated molecules that are reduced by the assistance of an additional molecule (methanol or hemiacetal product). The reactions catalyzed by the hemiacetal products show higher barriers than the one catalyzed by methanol. Copyright © 2012 John Wiley & Sons, Ltd.     

An indirect hybrid sound transmission loss controller

The control of sound transmission through panels is an important noise control problem in the aerospace, aeronautical, and automotive industries. The trend towards using lightweight composite materials that have lower sound insulation performance is a negative factor regarding low frequency transmission loss. Double-panel partitions with the gap filled with sound absorption materials are often employed to improve the sound insulation performance with reduced added weight penalty. However, in the low frequency range, the strong coupling between the panels through the air cavity and mechanical paths may greatly reduce the sound transmission performance, making it even lower than the performance of a single panel in some frequency ranges. In this work, an experimental investigation of a new kind of hybrid (active/passive) acoustic actuator is presented. The idea consists of replacing the acoustic absorption material by a hybrid actuator aiming at improving the transmission loss at low frequencies without altering the passive attenuation. A prototype of the system is tested in a plane wave acoustic tube setup. Different kinds of SISO feedforward control implementations were used to attenuate the sound power transmitted through the hybrid active–passive panel using an error microphone or a particle velocity sensor placed downstream with respect to the sample panel. Measurement results of the transmission loss with active and hybrid attenuation are presented and discussed.     

Spin disorder scattering in magnetic metallic alloys

Anomalous behavior of the resistivity at or just below the Néel temperature in antiferromagnetic metals is usually attributed to the formation of superzone gaps. However, we find that RMn12-xFex alloys which have no such gaps exhibit a similarly anomalous resistivity. We show that electron scattering by substitutional spin disorder can account for such behavior of itinerant magnets. This mechanism, which has not been studied before, leads to a relaxation rate that is proportional to x(12-x)m(2), where m is the staggered magnetization. Together with spin fluctuations, phonon, and impurity scattering, it accounts well for the resistivity data we obtain for HoMn12-xFex, for 0< or =x< or =9, in the temperature range of 4 to 400 K.     

Experimental and theoretical study of the mechanism for the kinetic of elimination of methyl carbazate in the gas phase

The elimination kinetic of methyl carbazate in the gas phase was determined in a static system over the temperature range of 340–390 °C and pressure range of 47–118 Torr. The reaction is homogeneous, unimolecular, and obeys a first order rate law. The decomposition products are methyl amine, nitrous acid, and CO gas. The variation of the rate coefficients with temperatures is given by the Arrhenius expression: log k₁ (s^?1) = (11.56 ± 0.34) ? (180.7 ± 4.1) kJ mol^?1(2.303 RT)^?1. The estimated kinetics and thermodynamics parameters are in good agreement to the experimental values using B3LYP/6‐31G (d,p), and MP2/6‐31G (d,p) levels of theory. These calculations imply a molecular mechanism involving a concerted non‐synchronous quasi three‐membered ring cyclic transition state to give an unstable intermediate, 1,2‐oxaziridin‐3‐one. Bond order analysis and natural charges implies that polarization of O (alkyl)? C (alkyl) bond of the ester is rate determining in this reaction. Copyright © 2008 John Wiley & Sons, Ltd.     

Origin of Fluorescence Lifetimes in Human Serum Albumin. Studies on Native and Denatured Protein

Human serum albumin consists of a single polypeptide of 585 amino acid residues with 1 Trp residue. In the present work, we measured fluorescence lifetimes of the protein in both native and denatured states. The results indicate that Trp emission occurs with three lifetimes in both states. Lifetimes values and contribution to the global emission decay differ between the two states. Data are interpreted as the results of an emission occurring from three substructures of the tryptophan formed in the excited state. Two of these substructures are already present for the tryptophan free in solution. The third lifetime is the result of the interaction between the tryptophan residue and surrounding microenvironment. The populations of these substructures characterized by the pre-exponential parameters of the fluorescence lifetimes are dependent on the fluorophore microenvironment and on the global protein structure.