EPR-detected photoinduced electron transfer in three structurally related molecular triads

A comparative electron paramagnetic resonance (EPR) study has been performed on a series of structurally related molecular triads which undergo photoinduced electron transfer and differ one from the other in terms of the acceptor or donor moieties. The molecular triads, C-P-C₆₀, TTF-P-C₆₀ and C-P-P_F, share the same free-base, tetraarylporphyrin (P) as the primary electron donor, which after light excitation initiates the electron transfer process, but differ either in terms of the electron acceptor (fullerene derivative, C₆₀, versus fluorinated free-base porphyrin, P_F), or in terms of the final electron donor (carotenoid polyene, C, versus tetrathiafulvalene, TTF). All these molecular triads can be considered artificial photosynthetic reaction centers in their ability to mimic several key properties of the reaction center primary photochemistry. Photoinduced charge separation and recombination have been followed by time-resolved EPR in a glass of 2-methyltetrahydrofuran and in the nematic phase of the uniaxial liquid crystal E-7. All the triads undergo photoinduced electron transfer, with the generation of charge-separated states in both the low-dielectric environment of the 2-methyl-tetrahydrofuran glass and in anisotropic E-7 medium. Different photochemical pathways have been recognized depending on the specific donor and acceptor moieties constituting the molecular triads. In the presence of the tetrathiafulvalene electron donor singlet- and triplet-initiated electron transfer routes are concurrently active. Recombination to the low-lying carotenoid triplet state occurs in the carotene-based triads, while singlet recombination is the only active route for the TTF-P-C₆₀ triad, where a low-lying triplet state is lacking. Long-lived charge separation has been observed in the case of TTF-P-C₆₀: about 8 μs for the singlet-born radical pair in the glassy isotropic matrix and about 7 μs for the triplet-born radical pair in the nematic phase of E-7. For all the molecular triads, a weak exchange interaction (J?1 G) between the electrons in the final spin-correlated radical pair has been evaluated by simulation of the EPR spectra, providing evidence for superexchange electronic interactions mediated by the tetraarylporphyrin bridge.     

Smart Geodesic Tracing in GRworkbench

We have developed a new tool for numerical work in General Relativity: GRworkbench. We discuss how GRworkbench's implementation of a numerically-amenable analogue to Differential Geometry facilitates the development of robust and chart-independent numerical algorithms. We consider, as an example, geodesic tracing on two charts covering the exterior Schwarzschild space-time.     

Une formule de Landau–Zener pour un croisement non dégénéré et involutif de codimension 3Landau–Zener formula for non-degenerate involutive codimension 3 crossings

In this Note, we study a 2×2 system of evolution equations with some codimension 3 crossing. We derive two conditions of non-degeneracy. We focus on one of them and reduce our system to some Landau–Zener's type system. Using this reduction, we describe the energy transfer at the crossing by Landau–Zener formula for 2-scales semi-classical measures. To cite this article: C. Fermanian Kammerer, P. Gérard, C. R. Acad. Sci. Paris, Ser. I 335 (2002) 915–920.     

On the Reality of the Eigenvalues for a Class of -Symmetric Oscillators

 We study the eigenvalue problem with the boundary conditions that decays to zero as z tends to infinity along the rays , where is a real polynomial and . We prove that if for some we have for all , then the eigenvalues are all positive real. We then sharpen this to a larger class of polynomial potentials. In particular, this implies that the eigenvalues are all positive real for the potentials when with , and with the boundary conditions that decays to zero as z tends to infinity along the positive and negative real axes. This verifies a conjecture of Bessis and Zinn-Justin. Received: 16 January 2002 / Accepted: 1 May 2002 Published online: 6 August 2002     

Structural evolution in amorphous silicon and germanium thin films.

The structural evolution in amorphous silicon and germanium thin films has been investigated by high-resolution transmission electron microscopy (HRTEM) in conjunction with autocorrelation function (ACF) analysis. The results established that the structure of as-deposited semiconductor films is of a high density of nanocrystallites embedded in the amorphous matrix. In addition, from ACF analysis, the structure of a-Ge is more ordered than that of a-Si. The density of embedded nanocrystallites in amorphous films was found to diminish with annealing temperature first, then to increase. The conclusions also corroborate well with the results of diminished medium-range order in annealed amorphous films determined previously by a variable coherence microscopy method.     

Barotropic Instability of the Bickley Jet at High Reynolds Numbers

We investigate the linear stability of the Bickley jet in the framework of the beta-plane approximation. Because singular inviscid neutral modes exist in the retrograde case     , it is necessary to add viscosity to interpret them. One of these modes was found in closed form by Howard and Drazin [1] . However, its critical point is at the center of the jet and it was therefore not possible for these authors to ascertain the relationship of this mode to the stability problem or to discuss how to continue the eigenfunction across the singularity.
The viscous critical layer problem associated with this singularity is considerably more difficult than the usual one (which leads to integrals of the Airy function) because     and, consequently, a second-order turning point is involved. Our analysis shows that the Howard–Drazin mode is degenerate in the domain where it is valid as a limit of the viscous problem (wavenumber  α²≤ 9/2  ), that is, it corresponds to both an odd and an even mode. This conclusion is confirmed by direct numerical solution of the Orr–Sommerfeld equation which shows, in addition, that viscosity is destabilizing along portions of the stability boundary. For a retrograde jet, instability is found to occur beyond the inviscid critical value of β, that is, in the region where the flow would be stable according to the Rayleigh–Kuo condition.     

MODEL COMPARISON FOR ACOUSTIC SCATTERING BY A SPHERICAL AIR BUBBLE IN WATER

The oscillation of a bubble has many vibrational modes, contributing to different portions in acoustic scattering. Without approximations a priori, an hydrodynamic approach is applied to investigate acoustic scattering by a bubble in water, taking into account the heat exchange and viscosity. The scattering function is derived for a wide range of frequencies. Examples are shown to illustrate the thermal and viscous effects on sound scattering. Comparison is made with three existing models. While these models are known not to be applicable for high frequencies, it is shown here that even in the low-frequency region, there are also noticeable discrepancies between the exact solution and the three existing models with regard to the scattering properties such as the scattering cross-section, and the quality factor of resonant peaks. By numerical simulation, we claim that the discrepancies may be due to the incomplete consideration of the thermal exchange process in the previous models. The approach presented here is valid for any other fluid enclosure in liquids.     

Magnetic properties of oxygenated carbon nitride films from RF-discharge in an acetylene, nitrogen, and oxygen mixture environments

Properties of oxygenated carbon nitride films have attracted the attention of physics researchers due to their magnetic and physical properties, as well as for their usefulness in the industry. The free radicals were investigated using electron paramagnetic resonance applied in the study of spin concentration due to the different mechanism of preparation of carbon nitride films by RF-discharge with different kinds of plasma. Unpaired spin concentrations, in the order of 10²⁰ per cm³, were measured and their time recombination dependency was important in those films. The films were grown by plasma enhanced chemical vapor deposition using mixtures of hydrocarbons, N₂ and O₂ in different proportions.     

A comprehensive study of the long pulse Nd:YAG laser drilling of multi-layer carbon fibre composites

The results of an extensive experimental study of the free running Nd:YAG laser drilling of a multi-layer carbon fibre composite, where adjacent layers have differently orientated fibres, are reported. For holes drilled with the laser operating in fixed-Q mode at 1064 nm, parallel sections of blind holes illustrating discontinuities in the hole size along a given section direction will be shown to occur at the interface between adjacent layers. An explanation for this effect is proposed. Detailed single pulse drilling characteristics will be presented illustrating the exit hole diameter as a function of pulse energy and material thickness. These characteristics illustrate a ‘stable' drilling regime in which the exit hole diameters are least sensitive to changes in pulse energy or material thickness and a less ‘stable' regime in which they are more strongly dependent on these parameters. Drilling characteristics will be given for two different beam qualities, illustrating the greater drilling depth and reduced hole size achievable with an improved beam quality. Finally holes drilled through a 2 mm thick sample of material with multiple pulses are considered. Size distribution curves for entrance and exit holes will be presented. The total energy required (number of pulses × pulse energy) to drill through 2 mm thick material will be reported as a function of pulse energy in stationary air and argon atmospheres and in a partial vacuum, illustrating a threshold energy which is dependent upon the drilling atmosphere. The threshold energies will be discussed with reference to plasma formation and the reactivity of the drilling atmosphere.