Cascaded highly nondegenerate four-wave-mixing phenomenon in transparent isotropic condensed media

Broad-bandwidth light pulses with different frequencies, extending from the IR to the UV, are simultaneously generated when two noncollinear, ultrafast laser pulses from a visible dual-frequency laser propagate through bulk isotropic transparent media such as common glass. This phenomenon, which is believed to have been previously unreported, can be explained by a cascade of highly nondegenerate four-wave-mixing processes and corresponds to a coherent scattering effect with geometrically minimized phase mismatch. Frequency-upconverted beams were observed up to the 11th order.     

Powder MAS NMR lineshapes of quadrupolar nuclei in the presence of second-order quadrupole interaction

We derive a complete analytical solution for the powder magic angle spinning (MAS) nuclear magnetic resonance (NMR) lineshape in the presence of second-order quadrupole interaction, considering a radiofrequency (rf) pulse of finite width, a finite MAS frequency, and a non-zero asymmetry parameter. I_x is calculated using two approaches. The first applies time-dependent perturbation theory in the presence of the rf pulse and stationary perturbation theory (SPT) in its absence. The second is based on the Magnus expansion of the density matrix in the interaction representation during the pulse and SPT in its absence. We solve the problem in the laboratory frame using the properties of the Fourier transform and spin operators. Diagonalisation is not required. Both approaches agree well with each other under all conditions and also with the transition probability approach for the central transition. The Magnus expansion exists at all times and the effect of the non-secular terms is negligible. We describe an analytical method of averaging I_x over the Euler angles and simulate the ¹¹B MAS NMR lineshapes for crystalline and vitreous B₂O₃. A critical analysis is given of all earlier calculations of the MAS NMR lineshape.     

Detection of susceptibility effects using simultaneous T(2)* and magnetic field mapping

Tracking susceptibility effects is a convenient way to detect small inclusions in a bulk tissue matrix by MRI. We propose a quantitative assessment of these susceptibility effects by simultaneously mapping T(2)* and magnetic field from the time course of magnitude and phase using a multiple GE sequence at 4.7 T. A high-pass scheme is also introduced to highlight the mesoscopic magnetic field variations due to local susceptibility differences specifically in the magnetic field map. Applying this method to muscle tissue, we demonstrate that connective tissue generates detectable susceptibility effects through concomitant local magnetic field variation and T(2)* shortening.     

Electromagnetic wave propagation through frequency-dispersive and lossy double-negative slab

This study presents the electromagnetic wave propagation through the frequency-dispersive and lossy double-negative slab embedded between two different semi-infinite media. The double-negative slab is realized by using two models, the Lorentz and Drude medium models. The properties and the required equations for the frequency-dispersive and lossy double-negative slab, the Lorentz medium and Drude medium are given in detail. After the construction of the problem, the reflection and transmission coefficients are derived for both TE and TM waves. Then, the reflected, transmitted and loss powers are determined using these coefficients. Finally, in the numerical results, the mentioned powers for TE and TM waves are computed and illustrated as a function of the incidence angle, the frequency and the slab thickness when the damping frequency changes.     

The unfair consequences of equal opportunities: Comparing exchange models of wealth distribution

Simple agent based exchange models are a commonplace in the study of wealth distribution of artificial societies. Generally, each agent is characterized by its wealth and by a risk-aversion factor, and random exchanges between agents allow for a redistribution of the wealth. However, the detailed influence of the amount of capital exchanged has not been fully analyzed yet. Here we present a comparison of two exchange rules and also a systematic study of the time evolution of the wealth distribution, its functional dependence, the Gini coefficient and time correlation functions. In many cases a stable state is attained, but, interesting, some particular cases are found in which a very slow dynamics develops. Finally, we observe that the time evolution and the final wealth distribution are strongly dependent on the exchange rules in a nontrivial way.     

Investigation of N‐carbamoylamino acid nitrosation by {NO + O2} in the solid‐gas phase. Effects of NOx speciation and kinetic evidence for a multiple‐stage process

Nitrosation of N‐carbamoylamino acids (CAA) by gaseous NO + O₂, an interesting synthetic pathway to amino acid N‐carboxyanhydrides (NCA), alternative to the phosgene route, was investigated on N‐carbamoyl‐valine either in acetonitrile suspension or solventless conditions, and compared to the classical nitrosating system NaNO₂ + CF₃COOH (TFA), the latter being quite less efficient in terms of either rate, stoichiometric demand, or further tractability of the product. The rate and efficiency of the NO + O₂ reaction mainly depends on the O₂/NO ratio. Evaluation of the contribution of various nitrosating species (N₂O₃, N₂O₄, HNO₂) through stoichiometric balance showed the reaction to be effected mostly by N₂O₃ for O₂/NO ratios below 0.3, and by N₂O₄ for O₂/NO ratios above 0.4. The relative contribution of (subsequently formed) HNO₂ always remains minor. Differential scanning calorimetry (DSC) monitoring of the reaction in the solid phase by either HNO₂ (from NaNO₂ + TFA), gaseous N₂O₄ or gaseous N₂O₃, provides the associated rate constants (ca. 0.1, 2 and 10⁸ s^?1 at 25°C, respectively), showing that N₂O₃ is by far the most reactive of these nitrosating species. From the DSC measurement, the latent heat of fusion of N₂O_3, 2.74 kJ · mol^?1 at ?105 °C is also obtained for the first time. The kinetics was investigated under solventless conditions at 0°C, by either quenching experiments or less tedious, rough calorimetric techniques. Auto‐accelerated, parabolic‐shaped kinetics was observed in the first half of the reaction course, together with substantial heat release (temperature increase of ca. 20°C within 1–2 min in a 20‐mg sample), followed by pseudo‐zero‐order kinetics after a sudden, important decrease in apparent rate. This kinetic break is possibly due to the transition between the initial solid‐gas system and a solid‐liquid‐gas system resulting from water formation. Overall rate constants increased with parameters such as the specific surface of the solid, the O₂/NO ratio, or the presence of moisture (or equivalently the hydrophilicity of the involved CAA), however without precise relationship, while the last two parameters may directly correlate to the increasing acidity of the medium. Copyright © 2007 John Wiley & Sons, Ltd.     

Energetic and structural characterization of 2‐R‐3‐methylquinoxaline‐1,4‐dioxides (R = benzoyl or tert‐butoxycarbonyl): experimental and computational studies

The gaseous standard molar enthalpies of formation of two 2‐R‐3‐methylquinoxaline‐1,4‐dioxides (R = benzoyl or tert‐butoxycarbonyl), at T = 298.15 K, were derived using the values for the enthalpies of formation of the compounds in the condensed phase, measured by static bomb combustion calorimetry, and for the enthalpies of sublimation, measured by Knudsen effusion, using a quartz crystal oscillator. The three dimensional structure of 2‐tert‐butoxycarbonyl‐3‐methylquinoxaline‐1,4‐dioxide has been obtained by X‐ray crystallography showing that the two N? O bond lengths in this compound are identical. The experimentally determined geometry in the crystal is similar to that obtained in the gas‐phase after computations performed at the B3LYP/6‐311 + G(2d,2p) level of theory. The experimental and computational results reported allow to extend the discussion about the influence of the molecular structure on the dissociation enthalpy of the N? O bonds for quinoxaline 1,4‐dioxide derivatives. As found previously, similar N? O bond lengths in quinoxaline‐1,4‐dioxide compounds are not linked with N? O bonds having the same strength. Copyright © 2007 John Wiley & Sons, Ltd.     

Thermal stability of alkoxy monolayers grafted on Si(1 1 1)

Direct grafting of organic monolayers on Si is of prime interest in order to give specific properties to a silicon surface. However, for microelectronics applications, this possibility is hampered by the limited stability of the grafted layers. It has been previously established that alkyl layers attached to Si surfaces through Si-C bonds become unstable at 250-300 °C, by desorption of alkenes. Changing the nature of the bonding to the surface might allow one to circumvent this desorption pathway and increase the layer stability. In our work, decanol and decyl aldehyde are reacted with the Si(1 1 1)-H surface at ∼100 °C during 20 h in order to obtain alkoxy monolayers. FTIR measurements performed in ATR geometry show that the grafted molecule surface coverage is on the order of 33% after reaction with decanol and 50% after reaction with decyl aldehyde. Characterization by AFM essentially reveals that the morphology of the grafted surfaces is unaffected as compared to that of Si-H surfaces. However, the edges of the terraces at alcohol-grafted surfaces exhibit some pitting, probably due to the presence of water in the grafting liquid. Thermal stability studies show that alkoxy chains progressively disappear from the Si surface between 200 and 400 °C. From the CH₂/CH₃ ratio in the CH region (2760-3070 cm⁻¹), it appears that the chains undergo progressive dissociation by C-C bond breaking before their complete disappearance from the surface. Therefore, the thermal behaviour of alkoxy monolayers appears quite distinct from that of alkyl monolayers that tend to leave the surface in a much narrower temperature range (250-350 °C), essentially via breaking of the Si-C bonds.     

Simultaneous measurement of anomalous group-velocity dispersion and nonlinear coefficient in optical fibers using soliton-effect compression

We present a novel and simple method to measure both the value of the second-order dispersion coefficient and the nonlinear coefficient in optical fibers. This method is based on the higher-order soliton-effect pulse compression phenomenon and is valid for dispersion values greater than 0.5 ps/km/nm. A non-zero dispersion-shifted fiber, a standard single-mode fiber and a highly-dispersive highly-nonlinear fiber have been measured using this method.