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This paper presents both experimental and modeling investigations of a catalytic wall fuel processor consisting of coupled methane reforming and methane combustion sections. The reacting systems are both catalytic and the latter generates the heat required for the occurrence of the former. The catalytic wall reactor was examined for light-off behavior and for steady-state product distribution. On one hand, the analysis of the reaction products distribution after catalyst ignition indicated that in both combustion and reforming sections catalysts undergo to a relatively long transient (about 40 min) before reaching steady state conditions. On the other hand, a much longer reactor thermal transient was observed and the two transient behaviors appear independent of each other. Analysis of the reactor operating under real conditions (nonadiabatic) showed that a 3D model is needed to accurately predict the reactor performance because a 2D model, although much more convenient, cannot allow for the whole heat loss thereby yielding unreliable results. [ABSTRACT FROM AUTHOR]

The development of spin-coupled diabatic representations for theoretical semiclassical treatments of photodissociation dynamics is an important practical goal, and some of the assumptions required to carry this out may be validated by applications to simple systems. With this objective, we report here a study of the photodissociation dynamics of the prototypical HBr system using semiclassical trajectory methods. The valence (spin-free) potential energy curves and the permanent and transition dipole moments were computed using high-level ab initio methods and were transformed to a spin-coupled diabatic representation. The spin−orbit coupling used in the transformation was taken as that of atomic bromine at all internuclear distances. Adiabatic potential energy curves, nonadiabatic couplings and transition dipole moments were then obtained from the diabatic ones and were used in all the dynamics calculations. Nonadiabatic photodissociation probabilities were computed using three semiclassical trajectory methods, namely, coherent switching with decay of mixing (CSDM), fewest switches with time uncertainty (FSTU), and its recently developed variant with stochastic decoherence (FTSU/SD), each combined with semiclassical sampling of the initial vibrational state. The calculated branching fraction to the higher fine-structure level of the bromine atom is in good agreement with experiment and with more complete theoretical treatments. The present study, by comparing our new calculations to wave packet calculations with distance-dependent ab initio spin−orbit coupling, validates the semiclassical trajectory methods, the semiclassical initial state sample scheme, and the use of a distance-independent spin−orbit coupling for future applications to polyatomic photodissociation. Finally, using LiBr +as a model system, it is shown that accurate spin-coupled potential curves can also be constructed for odd-electron systems using the same strategy as for HBr. [ABSTRACT FROM AUTHOR]

The article presents a tutorial on the isolated system with an internal adiabatic piston with regards to calculating and visualizing the thermodynamic equilibrium. It discusses the evolution towards mechanical or thermal equilibrium of the isolated system and the impossibility of predicting the final state based on classical equilibrium thermodynamics principles. It proposes several activities which constitute a good practice of fundamental principles of thermodynamics, which include the first and second laws, gas relations, entropy changes, which demands the visualization of physical processes. It concludes that there is spontaneous evolution towards mechanical equilibrium between the system and the processes, but not necessarily towards temperature equilibrium.

We report the results of studies of various aspects of the counter diabatic field paradigm, a recipe that generates adiabatic population transfer between levels by assisting a given field so that the total field generates the population transfer that the adiabatic approximation suggests for the given field. The sensitivity of this recipe to the pulse parameters and to Gaussian stochastic phase fluctuations between the fields has been investigated. Ladder-climbing population transfer between the vibrational levels of a nonrotating Morse oscillator is examined, and a numerical demonstration of the efficiency of the scheme is given. [ABSTRACT FROM AUTHOR]