Time Evolution of Vibration-Induced Excited State Decay

A simple model consisting of two electronic levels and one vibrational mode (phonon) was theoretically studied. The electronic-vibrational interaction was linear in the vibrational displacement. The vibrational mode was taken in the harmonic approximation and was attached to the thermal bath formed by the ambient environment. The kinetic constants of the vibrational dissipation were of the second order in the vibrational-bath coupling and were taken in the Markovian limit. Although, depending on the parameters of the model, different curves of the non-radiative vibration-induced excited state decay were obtained, in general, three time intervals, corresponding to different physical behaviour, were found. In the short-time interval, small oscillations superimposed on the excited state decay were observed. They were determined by the vibrational frequency and influenced by electronic-vibrational coupling. In the middle-time interval, almost quasi-exponential decay was detected; its rate constant increased with stronger electronic-vibrational interaction and speed of vibrational relaxation. In the long-time interval, the decay was very slow and, under special conditions, even an asymptotic non-zero excited state population was observed. Its value increased with the strength of the off-diagonal electron-vibrational coupling. Links of the parameters of the model with quantum chemical terms were estimated.     

Towards the Evaluation of the Relevant Degrees of Freedom in Nonlinear Partial Differential Equations

We investigate an operator renormalization group method to extract and describe the relevant degrees of freedom in the evolution of partial differential equations. The proposed renormalization group approach is formulated as an analytical method providing the fundamental concepts of a numerical algorithm applicable to various dynamical systems. We examine dynamical scaling characteristics in the short-time and the long-time evolution regime providing only a reduced number of degrees of freedom to the evolution process.     

Une nouvelle méthode de raffinement de maillage spatio-temporel pour l'équation des ondes

In the present Note we introduce an extension of the conservative space–time mesh refinement method presented by Fouquet et al. We also propose a post-treatment of the solution that reduces the spurious phenomena due to the non-conformity between the time meshes. A reinterpretation of the equations in terms of new unknowns leads to a new scheme with second order consistent coupling equations. Numerical experiments in 2D and a plane wave analysis for the 1D model show that the method is second order accurate for an arbitrary refinement. To cite this article: J. Rodríguez, C. R. Acad. Sci. Paris, Ser. I 339 (2004).     

Hamiltonian N2‐locally connected claw‐free graphs

A graph G is N₂‐locally connected if for every vertex ν in G, the edges not incident with ν but having at least one end adjacent to ν in G induce a connected graph. In 1990, Ryjá?ek conjectured that every 3‐connected N₂‐locally connected claw‐free graph is Hamiltonian. This conjecture is proved in this note. © 2004 Wiley Periodicals, Inc. J Graph Theory 48: 142–146, 2005     

A lithium ethyl­ene­diphos­phon­ate containing lithium chains and symmetric hydrogen bonds

In the title compound, catena‐poly[lithium‐μ₃‐ethyl­ene­diphos­phon­ato], [Li(C₂H₇O₆P₂)]_n, the supra­molecular monoclinic (C2/c) structure consists of one‐dimensional lithium chains [Li⋯Li = 2.7036 (8) Å] that are embedded within ethyl­ene­diphosphon­ate anions linked by strong symmetric hydrogen bonds [O⋯O = 2.473 (3) Å]. The Li atoms and the H atom in the symmetric hydrogen bond reside on twofold rotation axes and there is an inversion center at the mid‐point of the C—C bond of the ethylenediphosphonate ligand.     

Elliptic equations with BMO coefficients in Reifenberg domains

The inhomogeneous Dirichlet problems concerning divergence form elliptic equations are studied. Optimal regularity requirements on the coefficients and domains for the W^1,p theory, 1 < p < ∞, are obtained. The principal coefficients are supposed to be in the John‐Nirenberg space with small BMO seminorms. The domain is a Reifenberg domain. These conditions for the W^1,p theory not only weaken the requirements on the coefficients but also lead to a more general geometric condition on the domains. In fact, these domains might have fractal dimensions. © 2004 Wiley Periodicals, Inc.     

Evidence of a Photo‐Radical Pathway Responsible of the Rearrangement of a Manganese(III)‐Schiff Base Complex in Solution

A new Mn^III‐Schiff base complex, [MnL(OH₂)](ClO₄) ( 1 ) (H₂L = N, N′‐bis‐(3‐Br‐5‐Cl‐salicylidene)‐1, 2‐diimino‐2‐methylethane), an inorganic model of the catalytic center (OEC, Oxygen Evolving Complex) in photosystem II (PSII), has been synthesized and characterized by elemental analysis, IR and EPR spectroscopy, mass spectrometry, magnetic susceptibility measurement and the study of its redox properties by cyclic and normal pulse voltammetry. This complex mimics reactivity (showing a relevant photolytic activity), and also some structural characteristics (parallel‐mode Mn^III EPR signal from partially assembled OEC cluster) of the natural OEC. The complex 1 was found to rearrange in solution into a crystallographically solved square‐pyramidal complex, [MnLL′] ( 2 ) (HL′ = 6‐bromo‐4‐chloro‐2‐cyanophenol), through a process, which probably liberates radical species (detected by EPR), and provokes a C—N bond cleavage in the ligand. A photo‐radical mechanism is discussed to explain this rearrangement.     

Crystallization and morphology of poly(vinylidene fluoride)/poly(3‐hydroxybutyrate) blends. I. Spherulitic morphology and growth by polarized microscopy

The development of the poly(3‐hydroxybutyrate) (PHB) morphology in the presence of already existent poly(vinylidene fluoride) (PVDF) spherulites was studied by two‐stage solidification with two separate crystallization temperatures. PVDF formed irregular dendrites at lower temperatures and regular, banded spherulites at elevated temperatures. The transition temperature of the spherulitic morphology from dendrites to regular, banded spherulites increased with increasing PVDF content. A remarkable amount of PHB was included in the PVDF dendrites, whereas PHB was rejected into the remaining melt from the banded spherulites. When PVDF crystallized as banded spherulites, PHB could consequently crystallize only around them, if at all. In contrast, PHB crystallized with a common growth front, starting from a defined site in the interfibrillar regions of volume‐filling PVDF dendrites. It formed by itself dendritic spherulites that included a large number of PVDF spherulites. For blends with a PHB content of more than 80 wt %, for which the PVDF dendrites were not volume‐filling, PHB first formed regular spherulites. Their growth started from outside the PVDF dendrites but could later interpenetrate them, and this made their own morphology dendritic. These PHB spherulites melted stepwise because the lamellae inside the PVDF dendrites melted at a lower temperature than those from outside. This reflected the regularity of the two fractions of the lamellae because that of those inside the dendrites of PVDF was controlled by the intraspherulitic order of PVDF, whereas that from outside was only controlled by the temperature and the melt composition. The described morphologies developed without mutual nucleating efficiency of the components. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 873–882, 2003