A paradigm shift in rate determining step from single electron transfer between phenylsulfinylacetic acids and iron(III) polypyridyl complexes to nucleophilic attack of water to the produced sulfoxide radical cation: a non‐linear Hammett

Mechanism of oxidative decarboxylation of phenylsulfinylacetic acids (PSAAs) by iron(III) polypyridyl complexes in aqueous acetonitrile medium has been investigated spectrophotometrically. An initial intermediate formation between PSAA and [Fe(NN)₃]³⁺ is confirmed from the observed Michaelis–Menten kinetics and fractional order dependence on PSAA. Significant rate retardation with concentration of [Fe(NN)₃]³⁺ is rationalized on the basis of coordination of a water molecule at the carbon atom adjacent to the ring nitrogen of the metal polypyridyl complexes by nucleophilic attack at higher concentrations. Electron‐withdrawing and electron‐releasing substituents in PSAA facilitate the reaction and Hammett correlation gives an upward ‘V’ shaped curve. The apparent upward curvature is rationalized based on the change in the rate determining step from electron transfer to nucleophilic attack, by changing the substituents from electron‐releasing to electron‐withdrawing groups. Electron‐releasing substituents in PSAA accelerate the electron transfer from PSAA to the complex and also stabilize the intermediate through resonance interaction leading to negative reaction constants (ρ). Conversely, electron‐withdrawing groups, while retarding the electron transfer exert an accelerating effect on the nucleophilic attack of H₂O which leading to low magnitude of ρ⁺ compared to high ρ^? values of electron‐releasing groups. Marcus theory is applied, and a fair agreement is seen with the experimental values. Copyright © 2016 John Wiley & Sons, Ltd.     

Hamilton–Jacobi equation,reaction action surface and the emergence of the force concept in chemical reaction dynamics

A combination of Hamilton–Jacobi equation and fast marching algorithm can be used to study reaction dynamics by converting the potential energy surface to a reaction action surface. The reaction action surface has been found to be an important tool in theoretical chemistry, allowing us to provide a different force-based perspective of chemical reactions. Several properties such as reaction force, reaction force surface, reaction path force and reaction path force constant have been defined and calculated by using the reaction action surface. This paper investigates these newly defined properties in order to understand the role they play in chemical reaction with reference to a model 4-well potential energy surface.     

Inertial clustering of particles in high-Reynolds-number turbulence

We report experimental evidence of spatial clustering of dense particles in homogenous, isotropic turbulence at high Reynolds numbers. The dissipation-scale clustering becomes stronger as the Stokes number increases and is found to exhibit similarity with respect to the droplet Stokes number over a range of experimental conditions (particle diameter and turbulent energy dissipation rate). These findings are in qualitative agreement with recent theoretical and computational studies of inertial particle clustering in turbulence. Because of the large Reynolds numbers a broad scaling range of particle clustering due to turbulent mixing is present, and the inertial clustering can clearly be distinguished from that due to mixing of fluid particles.     

On-line nuclear orientation and relaxation studies of Cs isotopes

The hyperfine field of CsFe has been measured to be (+)40.8(0.7)T, using the technique of on-line low temperature nuclear orientation. The time dependent relaxation of¹²¹Cs^m Fe has also been investigated using a new technique, giving a Korringa constant C_k of 0.059 (15) sK. From this, an effective relaxation time of 3.0 (0.8)s can be deduced for the short lived¹¹⁸Cs^m(T_1/2=17s). This value has then been used to extract the magnetic moment of¹¹⁸Cs^m to be |μ|=5.4 (1.1) nm.     

A single-mode KrF laser

Single-mode operation of a KrF laser oscillator has been achieved for the first time. The laser medium is pumped by an electron beam which allows excitation for a much longer duration than with discharge pumping. The long excitation time, together with the use of a short oscillator cavity with a low single-pass gain, allows many roundtrips before saturation is reached. This makes line-narrowing easier and single-mode operation has been achieved using only two intracavity etalons.Technical Research Centre of Finland, Helsinki, Finland     

Influence of Data Acquisition Environment on Accuracy of Acoustic Voice Quality Measurements

Accuracy of acoustic voice analysis is influenced by the quality of recording. Lately, articles have suggested that soundcards perform equivalently to specialized professional-grade data acquisition (DA) systems. The purpose of this study was to investigate the influence of DA environment (DA system and microphone) on acoustic voice quality measurement (VQM) while balancing for gender, age, intersubject and intrasubject variability, and analysis software. More specifically, the relative performance of different hardware environments and the relationship between their technical characteristics and VQM performance was investigated. The discretization error and the effective dynamic range of the different DA environments were measured. We used 3 software systems to record and measure separately 2000 acoustic samples of sustained phonation for fundamental frequency, jitter, and shimmer. Analyses of variance (ANOVA) were performed with these parameters as the dependent variables. The results of the study suggested that professional-grade DA hardware is strongly recommended to provide accurate and valid voice assessment. The fundamental frequency measurement differences across DA environments were highly correlated to the discretization error (r=1.00), whereas jitter and shimmer were highly correlated to the effective dynamic range of the DA environments (r=-0.68 and r=-0.86, respectively).