A hydrogen-bonded dichloromethane-perchlorate-water channel in the crystal structure ofcis-[Ru(bpy)2{PPh-(o-tolyl)2}Cl+][ClO4 −]·CH2Cl2·H2O

The complexcis-[Ru(bpy)₂{PPh(o-tolyl)₂}Cl⁺][ClO₄ ^–] crystallized from a solution in dichloromethane as the dichloromethane-water solvate. The structure was refined toR=4.5% for those 2433 reflections with |F _o|>6(|F _o|). The octahedral Ru(II) cation is associated with metal-ligand distances as follows: Ru–Cl=2.434(3)Å, Ru-PPh(o-tol)₂=2.382(2)Å, and Ru–N=2.037(7)–2.088(7)Å. The structure is stabilized by a hydrogen-bonded CH₂Cl₂...ClO₄ ^–...H₂O channel which incorporates adventitious water of crystallization.     

X-ray diffraction studies oncis-[Ru(bpy)2(PMe3)Cl+][ClO4?] andcis-[Ru(bpy)2{PMe2(o-tol)}Cl+][ClO4?]; two ordered structures in thecis-bis(bipyridyl)chloro(phosphine)-ruthenium(II) series

The complexcis-[Ru(bpy)₂(PMe₃)Cl⁺][ClO₄ ⁻] crystallizes in space group P2₁/c andcis-[Ru(bpy)₂{PMe₂(o-tol)]Cl⁺][ClO₄ ⁻] crystallizes in space group ; each is present as a racemate and neither structure suffers from disorder. The Ru−PMe₂(o-tol) bond length of 2.324(2)? is slightly longer than the simple Ru−PMe₃ bond length of 2.310(2) ?.     

Globally convergent DC trust-region methods

In this paper, we investigate the use of DC (Difference of Convex functions) models and algorithms in the application of trust-region methods to the solution of a class of nonlinear optimization problems where the constrained set is closed and convex (and, from a practical point of view, where projecting onto the feasible region is computationally affordable). We consider DC local models for the quadratic model of the objective function used to compute the trust-region step, and apply a primal-dual subgradient method to the solution of the corresponding trust-region subproblems. One is able to prove that the resulting scheme is globally convergent to first-order stationary points. The theory requires the use of exact second-order derivatives but, in turn, the computation of the trust-region step asks only for one projection onto the feasible region (in comparison to the calculation of the generalized Cauchy point which may require more). The numerical efficiency and robustness of the proposed new scheme when applied to bound-constrained problems is measured by comparing its performance against some of the current state-of-the-art nonlinear programming solvers on a vast collection of test problems.     

Confined-acoustic-phonon-assisted cyclotron resonance via multi-photon absorption process in GaAs quantum well structure

Phonon-assisted cyclotron resonance (PACR) in GaAs quantum well (QW) structure is investigated via multi-photon absorption process when electrons interact with the confined acoustic phonon through deformation potential. The additional peaks in the absorption spectrum due to transitions between Landau levels accompanied with the emission and absorption of phonons are indicated. The dependence of absorption power on the temperature, magnetic field and well width is presented. Using profile method, we obtain PACR-linewidth as profiles of the curves. The temperature, magnetic field and well width dependences of the PACR-linewidth are investigated. The results are compared with those in the case of mono-photon absorption process, as well as in the electron-bulk acoustic phonon interaction. The results show that the multi-photon absorption process is strong enough to be detected in PACR.     

Both electron and hole Dirac cone states in Ba(FeAs)2 confirmed by magnetoresistance

Quantum transport of Dirac cone states in the iron pnictide Ba(FeAs)(2) with a d-multiband system is studied by using single crystal samples. Transverse magnetoresistance develops linearly against the magnetic field at low temperatures. The transport phenomena are interpreted in terms of the zeroth Landau level by applying the theory predicted by Abrikosov. The results of the semiclassical analyses of a two carrier system in a low magnetic field limit show that both the electron and hole reside as the high mobility states. Our results show that pairs of electron and hole Dirac cone states must be taken into account for an accurate interpretation in iron pnictides, which is in contrast with previous studies.     

Pyrazolin-4-ylidenes: a new class of intriguing ligands

The immense success of N-heterocyclic carbenes in recent years has initiated the search for even stronger ligands leading to the discovery of abnormal and remote NHCs. This article reflects our particular interest in the coordination chemistry of pyrazolin-4-ylidenes as a contribution to this field. A modular approach to 4-iodopyrazolium salts with different substitution patterns is described, which upon oxidative addition to Pd(0) gave rise to a library of new Pd(ii) pyrazolin-4-ylidene complexes. A preliminary study showed that selected complexes are active precatalysts in Suzuki-Miyaura and Mizoroki-Heck coupling reactions. The 3,5-substituents of pyrazolin-4-ylidenes are found to have significant effects on complexation and catalytic activities. Finally, the nature of this new class of ligands is discussed, and a future direction for further explorations in this exciting field is envisioned.     

Intensity‐dependent ultrafast dynamics of injection currents in unbiased GaAs quantum wells

The intensity dependence of optically‐induced injection currents in unbiased GaAs semiconductor quantum wells grown in [110] direction is investigated theoretically for a number of well widths. Our microscopic analysis is based on a 14 × 14 band k · p method in combination with the multisubband semiconductor Bloch equations. An oscillatory dependence of the injection current transients as function of intensity and time is predicted and explained. It is demonstrated that optical excitations involving different subbands and Rabi flopping are responsible for this complex dynamics. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A theoretical kinetic study of the reactions of NH2 radicals with methanol and ethanol and their implications in kinetic modeling

Amino (NH₂) radicals play a central role in the pyrolysis and oxidation of ammonia. Several reports in the literature highlight the importance of the reactions of NH₂ radicals with fuel in NH₃-dual-fuel combustion. Therefore, we investigated the reactions of NH₂ radicals with methanol (CH₃OH) and ethanol (C₂H₅OH) theoretically. We explored the various reaction pathways by exploiting CCSD(T)/cc-pV(T, Q)Z//M06-2X/aug-cc-pVTZ level of theory. The reaction proceeds via complex formation at the entrance and exit channels in an overall exothermic process. We used canonical transition state theory to obtain the high-pressure limiting rate coefficients for various channels over the temperature range of 300–2000 K. We discerned the role of various channels in the potential energy surface (PES) of NH₂ + CH₃OH/C₂H₅OH reactions. For both reactions, the hydrogen abstraction pathway at the OH-site of alcohols plays a minor role in the entire T-range investigated. By including the title reactions into an extensive kinetic model, we demonstrated that the reaction of NH₂ radicals with alcohols plays a paramount role in accurately predicting the low-temperature oxidation kinetics of NH₃-alcohols dual fuel systems (e.g., shortening the ignition delay time). On the contrary, these reactions have negligible importance for high-temperature oxidation kinetics of NH₃-alcohol blends (e.g., not affecting the laminar flame speed). In addition, we calculated the rate coefficients for NH₂ + CH₄ = CH₃ + NH₃ reaction that are in excellent agreement with the experimental data.