Interaction of rotationally aligned and of oriented molecules in gas phase and at surfaces

Recent developments concerning the generation of molecular beams containing oriented/aligned molecules will be reviewed and applications of such tools to the study of elementary processes occurring both in homogeneous and heterogeneous phases will be presented. First we will discuss the case of symmetric top molecules oriented by hexapoles. Here the molecular polarization is obtained by the use of an external field and allows to control which end of the molecular projectile is going to collide with the target. Then we will review the so-called collisional alignment, a molecular polarization phenomenon occurring in supersonic expansions of gaseous mixtures. The key feature, in this case, is the velocity dependence of the alignment degree, which allows the use of mechanical devices to filter out of the beam the molecules having either a random (statistical) or a preferential (non-statistical) spatial distribution of their rotational angular momentum J with respect to the molecular beam axis. The physical mechanisms underlying the collisional alignment will be resumed and some relevant gas-phase experiments demonstrating its occurrence will be illustrated. Application of such methodologies to the investigation of the stereodynamics of elementary processes occurring in gas-surface interaction will be presented and discussed for both weakly and strongly interacting systems.     

The electrochemical techniques for the diagnosis and restoration treatments of technical and industrial heritage: three examples of metallic artefacts

From technical and industrial heritage, curators are in charge of numerous and important collections of metallic items which are representative of the industrial and technical development of our societies. The diagnosis of the conservation state and the choice of the restoration treatment are important questions that have to be solved by curators to avoid expensive restoration works. This paper proposes to show how simple electrochemical techniques can be used as an efficient tool to contribute to the diagnosis of the conservation state of metallic artefacts and to monitor the restoration treatment through three examples. In the case of the very-corroded aluminium alloys of aircraft belonging to the Air and Space Museum (Le Bourget, France), stationary electrochemical measurements are able to characterise the allowable electrochemical effect of thick corrosion layer on the corrosion rate of metal but are not sufficient to give a complete diagnosis. In contrary, for the bronze part of the miner's lamp collection of the Mining History Centre of Lewarde, France and the nickel-plated steel of an ancient typewriter of the Musée des Arts et Metiers, Paris, France, an inhibition treatment based on sodium carboxylate within the framework of temporary conservation treatment was applied with success, on the basis of the electrochemical results obtained in the present study.     

Selection of suitable operating conditions to minimize the gradient equilibration time in the separation of drugs by Ultra-High-Pressure Liquid Chromatography with volatile (mass spectrometry-compatible) buffers

Reversed phase gradient elution is the method of choice for pharmaceuticals analysis since it allows reducing the analysis time while improving both the quality of the separation and the detection limits. The current trends are towards faster separations which can be achieved thanks to equipments withstanding ultra-high pressures and/or high temperatures. Under such conditions, gradient separations can be carried out within a few minutes or even a few tens of seconds. A long equilibration time in addition to the gradient time can be therefore very detrimental. In this work, we investigated the extent to which the gradient equilibration time can be reduced and which parameters mainly affect the retention variability of ionizable compounds when using volatile buffers. We first found out an excellent repeatability between run-to-run experiments whatever the equilibration time and the operating conditions. We then pointed out the key operating parameters which allow achieving reproducible runs when varying the equilibration time between runs. With a view of reducing the equilibration time, the effects of various conditions were examined. The latter include the type of additive for mobile phase pH adjustment, the initial eluent composition, the type of stationary phase, the temperature and the flow-rate. Although much remains to be understood about the equilibration process, our study allows making progress in the knowledge of this phenomenon. Based on the present results, a beneficial effect of both temperature and flow-rate was highlighted and operating conditions leading to faster column equilibration are suggested.     

The fractionary Schrödinger equation,Green functions and ultradistributions

In this work, we generalize previous results about the Fractionary Schrödinger Equation within the formalism of the theory of Tempered Ultradistributions. Several examples of the use of this theory are given. In particular we evaluate the Green function for a free particle in the general case, for an arbitrary order of the derivative index.     

Almost everywhere convex functions on R n and weak derivatives

The classical subdifferential calculus is a useful tool in order to establish characterizations of convex functions and optimality conditions; but it becomes useless when one thinks to study almost everywhere convex functions. In this paper by using Sobolev space theory we give some characterizations of this class of functions.     

Polariton-polariton kinematic interaction modulation and kinematic bipolaritons in organic microcavities

We study polariton-polariton kinematic interactions in organic microcavities. Using the Agranovich-Toshich transformation, to transform the Frenkel excitons from Paulions into Bosons, the exciton-exciton kinematic interaction is derived. In the strong coupling regime, the polariton excitonic part results in the polariton-polariton kinematic interaction. The scattering amplitude is calculated and the effective potential is obtained for a scattering between two free polaritons. The effective potential can be modulated by changing the exciton-cavity photon detuning, and we show the crossover of the effective potential from attractive into repulsive one. A pole in the two-particle Green's function is the signature of the formation of polariton bound state, i.e. bipolariton. Due to the smallness of the polariton effective mass, the obtained bound state is very shallow and appears below the minimum of the lower polariton branch, and falls inside the natural bandwidth of the polariton branch.     

Coherent states,phase states,and condensed states

We study phase properties of generalized coherent states obtained from usual Fock coherent states by adapting classical methods of statistical mechanics, in particular, the well-known procedure of thermodynamical limit. Moreover, we show that there exists a close connection between these states and the states describing boson systems with condensation properties.