An instrumented vehicle for offroad dynamics testing

The paper presents an instrumented vehicle that was equipped with measuring systems to perform complete dynamics tests, especially in off-road conditions. The equipment consists of four wheel dynamometers, a steering robot, and a differential GPS system together with an inertial platform, a non-contact vehicle speed sensor, and an on-board computer with software to control the devices and collect experimental data. The four wheel dynamometers measure six elements; based on strain gage force transducers, it measures three orthogonal forces and three moments. The steering robot can control the steering wheel of the vehicle at a variety of excitation modes; it can carry out typical vehicle dynamics tests (ISO 7401, ISO 4138, ISO/TR3888, etc.) as well as custom engineered tests at a wide range of setting parameters (steer angle rate up to 1600 deg/s). The differential GPS system gives true time vehicle kinematics data (velocities, accelerations, angles, etc.) at 10-ns sample rate and 20-mm accuracy. The base vehicle, a Suzuki Vitara 4 × 4, required no special modifications or changes to install the measuring equipment. The paper also describes typical tests performed with the use of the instrumented vehicle together with sample results.     

Upper tails for counting objects in randomly induced subhypergraphs and rooted random graphs

General upper tail estimates are given for counting edges in a random induced subhypergraph of a fixed hypergraph ℋ, with an easy proof by estimating the moments. As an application we consider the numbers of arithmetic progressions and Schur triples in random subsets of integers. In the second part of the paper we return to the subgraph counts in random graphs and provide upper tail estimates in the rooted case.     

Serre Problem for Unbounded Pseudoconvex Reinhardt Domains in ℂ<Superscript>2</Superscript>

We give a characterization of non-hyperbolic pseudoconvex Reinhardt domains in ℂ² for which the answer to the Serre problem is positive. Moreover, all non-hyperbolic pseudoconvex Reinhardt domains in ℂ² with non-compact automorphism group are explicitly described.     

Symmetry enforced gauge invariance of nuclear magnetic shielding constants

E.S.R. experiments performed at 1·3 K by optical detection are reported for the photo-excited triplet state of palladiumporphin in a single crystal of n-octane, and the observation of a level anticrossing signal is described.

In the crystal the orbital degeneracy of the ³ E _u state of the free molecule is lifted by the crystal field and in n-octane the energy difference between the two orbital components |x> and |y> is found to be 58 ± 2 cm^-1. The spinorbit coupling (SOC) and the orbital Zeeman interaction couple the triplet manifolds of |x> and |y>, and for a proper understanding of the magnetic properties of these states it is necessary to work in the basis of the six spin-orbit functions deriving from the ³ E _u state of the free molecule. It is shown that either of the two triplet states can be described by an effective spin hamiltonian of the common form and expressions for the zero-field parameters D and E and the principal values of the g tensor are given. The experimental values of the parameters in the lowest triplet state are D = -24·38 ± 0·03 GHz, |E| = 320 ± 60 MHz, g _‖ = 1·677 ± 0·001 and g _⊥ = 1·989 ± 0·002. The matrix element of the SOC connecting the |x> and |y> triplet manifolds amounts to qZ = 15 ± 3 cm^-1 and the vibronic orbital angular momentum (in units of ?) in the ³ E _u state of the free molecule to qΛ = 1·5 ± 0·3. A tentative value of 0·63 for the orbital reduction factor q is obtained by comparison with a theoretical estimate of Λ. The value of q is indicative of weak Jahn-Teller coupling.     

A stochastic model of the influence of buffer gas collisions on Mollow spectra

In this paper, using the idea introduced in (K. Wódkiewicz, Noise in strong laser-atom interaction, Proceedings of the VI International School of Coherent Optics, Ustron, Poland, September (1985) 19–26) and developed in (Cao Long Van, Stochastic Models of Isolated Collisions: Applications to Optical Phenomena, paper presented in LAMP Conference’89, Trieste, Italy (1989) II) we consider the influence of collisional fluctuations on the Mollow spectra of resonance fluorescence (RF). The fluctuations are taken into account by a simple shift of the constant detuning, involved in a set of optical Bloch equations by collision frequency noise which is modelled by a two-step random telegraph signal (RTS). We consider in detail the Mollow spectra for RF in the case of an arbitrary detuning of the laser frequency, where the emitter is a member of a statistical ensemble in thermodynamic equilibrium with the buffer gas at temperature T which is treated as a colored environment, and velocity v is distributed with the Maxwell-Boltzmann density.     

Plasmonic enhancement of blue emission from ZnO nanorods grown on the anodic aluminum oxide (AAO) template

Luminescent properties of ZnO nanorods covered with Ag nanoparticles are examined. Nanorods were synthesized on AAO templates using Atomic Layer Deposition (ALD) technique. Two types of the samples were prepared with different arrangement of ZnO nanorods and doping conditions. Nanorods of the second type were codoped with Al, to stimulate defect-related emissions. The ZnO material fills heterogeneously the interior of the AAO nanopores and has hexagonal, wurtzite structure. Both types of structures exhibit a broad defect-related emission at about 440 nm, most probably related to recombination at zinc interstitial (Zn_i) defects. This emission in samples with a random distribution of ZnO:Al nanorods and finer Ag nanoparticles is enhanced by factor of ～2.5 upon Ag deposition. The so-obtained material is interesting from the point of view of its application in blue range emitting diodes.     

Unravelling Structural Mysteries of Simple Organozinc Alkoxides

Simple RZnOR’ alkoxides are among the first known organozinc compounds, and widespread interest in their multifaced chemistry has been driven by their fundamental significance and potential applications including various catalytic reactions. Nevertheless, their chemistry in solution and in the solid state remains both relatively poorly understood and a subject of constant debate. Herein, the synthesis and structural characterization of long-sought structural forms, a roof-like trimer [(tBuZn)₃(μ-OC(H)Ph₂)₂(μ₃-OC(H)Ph₂)] and a ladder-type tetramer [(PhZn)₄(μ-OC(H)Ph₂)₂(μ₃-OC(H)Ph₂)₂], incorporating diphenylmethanolate as a model alkoxide ligand, are reported. Both novel aggregates are robust in the solid state and resistant towards mechanical force. By using ¹H NMR and diffusion-order spectroscopy, it is demonstrated that new RZnOR’ alkoxides are kinetically labile in solution and readily undergo ligand scrambling, such as in the case of Schlenk equilibrium. The elucidated key structural issues, which have remained undiscovered for decades, significantly advance the chemistry of RZnOR’ alkoxides and should support the rational design of zinc alkoxide-based applications.     

Stepwise Stress-Induced Transformations of Metal-Organic Polyhedral Cluster-Based Assemblies: Where Conformational and Supramolecular Features Meet

Understanding the factors governing the formation of supramolecular structures and phase transitions between various forms of molecular crystals is pivotal for developing dynamic, stimuli-responsive materials and polymorph-controlled syntheses. Here, we investigate the pressure-induced dynamic of both the intrinsic molecular structure and the supramolecular network of a predesigned polyhedral oxo-centered zinc cluster incorporating monoanionic N,N’-diphenylformamidinate and featuring N-bonded phenyl groups in close proximity to the primary coordination sphere. We demonstrate that the model oxo cluster is prone to undergoing pressure-induced conformational transformations of the secondary coordination sphere and simultaneous stepwise (initially every second polyhedral molecule undergoes the conformational transformations) and reversible transitions from an ambient phase α to high-pressure phases β and γ, as single-crystal-to-single-crystal events. The observed phase transitions illustrate the key role of an interplay between the low-energy conformation perturbations and cooperative intra- and intermolecular noncovalent interactions.     

Effectiveness of the Oxygenation over Classical Protonolysis Reactions: A Case of Alkylzinc Complexes Incorporating an Aminoalcoholate Ligand

Alkylzinc aminoalcoholates have emerged as powerful catalysts in organic synthesis and polymerization processes. Despite extensive research, difficulties in the rational design of these catalytic systems and in-depth understanding of their modes of action have hitherto been encountered. Most of the major obstacles stem largely from the relatively limited knowledge of the structure-activity relationship of zinc catalysts. In fact, the key active species are often generated in situ via the protonolysis of the alkylzinc precursors, which precludes their isolation and detailed characterization. Herein, the effectiveness of the oxygenation over the classical protonolysis in the synthesis of zinc alkylperoxides stabilized by an aminoalcoholate ligand is demonstrated. The controlled oxygenation of a tert-butylzinc complex incorporating a pridinolum (prinol) ligand leads to well-defined a dinuclear adduct of a (prinol)ZnOOtBu moiety with the parent tBuZn(prinol) complex and a novel dimer [tBuOOZn(prinol)]₂ with terminal alkylperoxide groups. The observed reaction outcomes strongly depend on the reaction conditions. Although sparse examples of heteroleptic adducts of the [RZn(L)]_x[ROOZn(L)]_y-type are known, the herein reported homoleptic [ROOZn(L)]_x aggregate is unprecedented. Strikingly, comparative studies involving reactions between tBuZn(prinol) and tert-butylhydroperoxide or ethanol revealed that the respective seemingly simple zinc alkylperoxides, or zinc alkoxides, respectively, are not accessible via the classical alcoholysis. We believe that these game-changing results concerning multifaceted chemistry of organozinc aminoalcoholates should pave the way for more rational development of various Zn-based catalytic systems.