Experimental and Theoretical Evidence of Spin-Orbit Heavy Atom on the Light Atom 1H NMR Chemical Shifts Induced through H⋅⋅⋅I− Hydrogen Bond

Spin-orbit (SO) heavy-atom on the light-atom (SO-HALA) effect is the largest relativistic effect caused by a heavy atom on its light-atom neighbors, leading, for example, to unexpected NMR chemical shifts of ¹H, ¹³C, and ¹⁵N nuclei. In this study, a combined experimental and theoretical evidence for the SO-HALA effect transmitted through hydrogen bond is presented. Solid-state NMR data for a series of 4-dimethylaminopyridine salts containing I⁻, Br⁻ and Cl⁻ counter ions were obtained experimentally and by theoretical calculations. A comparison of the experimental chemical shifts with those calculated by a standard DFT methodology without the SO contribution to the chemical shifts revealed a remarkable error of the calculated proton chemical shift of a hydrogen atom that is in close contact with the iodide anion. The addition of the relativistic SO correction in the calculations significantly improves overall agreement with the experiment and confirms the propagation of the SO-HALA effect through hydrogen bonds.     

Influence of Finite-Time Velocity Correlations on Scaling Properties of the Magnetic Field in the Kazantsev-Kraichnan Model: Two-Loop Renormalization Group Analysis

Theoretical and Mathematical Physics - Using the field theory renormalization group method and the operator product expansion technique in the two-loop approximation, we investigate the influence...     

Passive Advection in a Percolation Process: Two-Loop Approximation

Theoretical and Mathematical Physics - We study an instructive model of the directed percolation process near its second-order phase transition between absorbing and active states. We first express...     

Reversible C=C Bond Activation by an Intramolecularly Coordinated Antimony(I) Compound

The reaction of N,C,N-chelated stibinidene ArSb ( 1 ) (Ar=C₆H₃-2,6-(CH=NtBu)₂) with selected N-alkyl/aryl-maleimides RN(C(O)CH)₂ (R=Me, tBu, Ph) gave the addition products with bridged bicyclic [2.2.1] structure containing an antimony atom at the bridgehead position, fused with a 6-membered benzene and a 5-membered N-alkyl/aryl-pyrrolidine ring. These compounds were completely characterized. More importantly, additional studies showed that these reactions are reversible in solution, thereby representing an unprecedented reversible activation of a C=C bond by an antimony(I) compound.     

Disappearing Polymorphs in Metal–Organic Framework Chemistry: Unexpected Stabilization of a Layered Polymorph over an Interpenetrated Three-Dimensional Structure in Mercury Imidazolate

The “disappearing polymorph” phenomenon is well established in organic solids, and has had a profound effect in pharmaceutical materials science. The first example of this effect in metal-containing systems in general, and in coordination-network solids in particular, is here reported. Specifically, attempts to mechanochemically synthesize a known interpenetrated diamondoid (dia) mercury(II) imidazolate metal–organic framework (MOF) yielded a novel, more stable polymorph based on square-grid (sql) layers. Simultaneously, the dia-form was found to be highly elusive, observed only as a short-lived intermediate in monitoring solvent-free synthesis and not at all from solution. The destabilization of a dense dia-framework relative to a lower dimensionality one is in contrast to the behavior of other imidazolate MOFs, with periodic density functional theory (DFT) calculations showing that it arises from weak interactions, including structure-stabilizing agostic C−H⋅⋅⋅Hg contacts. While providing a new link between MOFs and crystal engineering of organic solids, these findings highlight a possible role for agostic interactions in directing topology and stability of MOF polymorphs.     

Wind turbine speed control of a contactless piezoelectric wind energy harvester

ABSTRACT

Wind turbine control is an important task to make the electricity generation secure in terms of energy demand and machine safety. It also yields to control the desired power level and optimized energy because of the assignment of turbine speed. The contactless piezoelectric wind energy harvester (CPWEH) used in this study has three piezoelectric layers located around the shaft with 120 degrees apart and they are buckled by the magnetic force without any physical contact. The superiority of this device is to generate energy for low wind speeds such as 1.5 m/s. However, for high speeds, high total harmonic distortions (THDs) govern the waveforms, thus controlling the turbine speed becomes necessary for optimizing the output power. Encouraged by this, a small low inertia dc generator is coupled with the wind turbine, and the generator terminals are connected to a resistor through a power switch to generate a braking torque that opposes to wind speed direction. By controlling the switch properly, turbine speed is ensured to remain within a certain band, which accordingly prevents the turbine from rotating very fast at damaging wind speeds. Several experiments are performed on the developed CPWEH with/without the presented control scheme which prove the existence of promising performance of our proposal.     

On the difference spaces of almost convergent and strongly almost convergent double sequences

In this paper, we study the difference spaces \({\mathcal {F}}(\varDelta )\), \({\mathcal {F}}_0(\varDelta )\), \({\mathcal {[F]}}(\varDelta )\) and \({\mathcal {[F]}}_0(\varDelta )\) of double sequences obtained as the domain of four-dimensional backward difference matrix \(\varDelta \) in the spaces \({\mathcal {F}}\), \({\mathcal {F}}_{0}\), \({\mathcal {[F]}}\) and \({\mathcal {[F]}}_{0}\) of almost convergent, almost null, strongly almost convergent and strongly almost null double sequences; respectively. We examine general topological properties of those spaces and give some inclusion theorems. Furthermore, we deal with their dual spaces.