Dynamical signatures of ‘phase transitions’: Chaos in finite clusters

Finite clusters of atoms or molecules, typically composed of about 50 particles (and often as few as 13 or even less) have proved to be useful prototypes of systems undergoing phase transitions. Analogues of the solid-liquid melting transition, surface melting, structural phase transitions and the glass transition have been observed in cluster systems. The methods of nonlinear dynamics can be applied to systems of this size, and these have helped elucidate the nature of the microscopic dynamics, which, as a function of internal energy (or ‘temperature’) can be in a solidlike, liquidlike, or even gaseous state. The Lyapunov exponents show a characteristic behaviour as a function of energy, and provide a reliable signature of the solid-liquid melting phase transition. The behaviour of such indices at other phase transitions has only partially been explored. These and related applications are reviewed in the present article.     

Application of a momentum method to some rarefied gas flow problems

Zusammenfassung Eine Kombination der Lees-Methode und des Mott-Smith Ansatzes wird auf zwei Probleme der Couette-Strömung zwischen zwei Zylindern angewandt. Es werden Ausdrücke hergeleitet für das Moment im Fall, dass ein Zylinder rotiert, und für den Wärmefluss im Fall, dass beide Zylinder stationär sind, aber verschiedene Temperatur haben; diese Ausdrücke sind für alle Werte der Knudsenzahl gültig.     

Classical trajectory analysis in atom—triatom collisions: Continuous quantization and scaling behaviour

A method of analysing classical trajectory data, based on recently derived scaling principles, is applied to a model atom-triatom collinear collision system. Apart from the utility of the scaling idea in extending trajectory computations, the analysis of the scaling coefficients in terms of transition probabilities increases the scope of the classical scaling theory as a means of obtaining (at the very least) qualitative quantum-mechanical information from classical trajectories. As an useful adjunct, the method of continuous quantization is applied to generate approximate transition probabilities. These results are semiquantitative; thus a combination of classical scaling and continuous quantization affords a powerful means of modeling complex collision cases with a minimum of computational effort.     

NQR Studies of the chloro(amino)cyclotriphosphazenes,N3P3(NHCH2·CH2NH)Cl4, N3P3(NHBut)4Cl4 and N3P3(NHBut)4Cl2

The frequencies and variable-temperature behaviour of ³⁵Cl nuclear quadrupole resonance in three aminocyclophosphazene derivatives are reported. The observed frequencies and multiplicity are correlated with the disposition of the substituents and the crystal structure. The temperature-dependence data are discussed in the framework of Bayer-Kushida-Brown equations and low-lying torsional (librational) frequencies and their average temperature coefficients are estimated. Brown's parabolic equation provides a good fit to the experimental data. Variable-temperature proton FT-NMR measurements (at 270 MHz) have also been carried out. The results are consistent with the NQR data and indicate the presence of two-site chemical exchange of the -NH protons and hydrogen bonding.     

A simple and inexpensive two channel boxcar integrator

It is shown that the inclusion of a small amount of primary ionisation makes the solution to the discharge equilibrium problem single valued.     

The Kirkendall Effect for Engineering Oxygen Vacancy of Hollow Co3O4 Nanoparticles toward High‐Performance Portable Zinc–Air Batteries

Structure and defect control are widely accepted effective strategies to manipulate the activity and stability of catalysts. On a freestanding hierarchically porous carbon microstructure, the tuning of oxygen vacancy in the embedded hollow cobaltosic oxide (Co₃O₄) nanoparticles is demonstrated through the regulation of nanoscale Kirkendall effect. Starting with the embedded cobalt nanoparticles, the concentration of oxygen‐vacancy defect can vary with the degree of Kirkendall oxidation, thus regulating the number of active sites and the catalytic performances. The optimized freestanding catalyst shows among the smallest reversible oxygen overpotential of 0.74 V for catalyzing oxygen reduction/evolution reactions in 0.1 m KOH. Moreover, the catalyst shows promise for substitution of noble metals to boost cathodic oxygen reactions in portable zinc–air batteries. This work provides a strategy to explore catalysts with controllable vacancy defects and desired nano‐/microstructures.