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.     

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.     

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.     

Rb saturation spectroscopy with an optically narrowed FM diode laser

A fast-frequency modulated (FM) diode laser has been optically narrowed using the technique of resonant optical feedback, to provide linewidths in each FM mode of ≈ 200 kHz peak-to-peak. With a drive frequency of 50 MHz and modulation index of 0.2, the FM laser has been used for the first time to obtain Doppler-free FM spectra of the Rb D₁ line at 795 nm. The potential use of this system for laser frequency stabilisation is discussed.     

The measurement of subcritical electroconvection

Under idealized conditions, electroconvection in a nematic liquid crystal sets in at a well-defined threshold of the driving ac voltage. Fluctuating convection rolls of a small amplitude below that threshold have been observed recently. The measurement of the amplitude of these fluctuations is described in detail in this paper. It is based on averaging the light intensity signals using the structure function and a quantitative analysis of the light deflection.     

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Book reviews

     

A biogenetically patterned enantiospecific synthesis of allopupukeanones

The first enantiospecific synthesis of allopupukeanones has been accomplished starting from 6-methylcarvone. A biogenetically patterned rearrangement of a pupukeanane to allopupukeanane was employed as the key step.     

C- and N-Amidotrichloroethylation of Azoles

1H-Pyrazoles, triazoles, and imidazoles in reaction with ethoxycarbonylimine and arylsulfonylimines of chloral yield addition products, corresponding 1-(1-amidotrichloroethyl)azoles. Derivatives of 1-alkylpyrazoles and pyrazolones react with chloral 4-chlorophenylsulfonylimine to furnish products of C-amidotrichloroethylation into position 4 of the azole ring.     

Fundamental processes in long air gap discharges

The development of atmospheric lightning is initiated and sustained by the formation in virgin air of ‘streamer corona’ and ‘leader’ discharges, very similar to those observed in laboratory long sparks. Therefore, the experimental and theoretical investigations of these laboratory discharges have become of large interest to improve the physical knowledge of the lightning process and to develop self-consistent models that could be applied to new protection concepts.In the present paper the fundamental processes of the subsequent phases of long air gap discharges are analyzed, from the first corona inception and development to the leader channel formation and propagation. For all these processes simulations models are discussed that have been essentially derived and simplified by the authors, in order to develop sequential time-dependent simulation of the laboratory breakdown, with both positive and negative voltages. The possibility of extending these models to the case of natural lightning is discussed in the companion paper, presented in this same volume. To cite this article: I. Gallimberti et al., C. R. Physique 3 (2002) 1335–1359.