Electronic and molecular structure of photoexcited [Ru(II)(bpy)3]2+ probed by picosecond X-ray absorption spectroscopy

L(2,3) X-ray absorption spectra of aqueous [Ru(II)(bpy)3]2+ have been recorded in its ground and excited states, 50 ps after short pulse laser excitation. Significant changes in both the XANES (X-ray Near-Edge Absorption Structure) and the EXAFS (Extended X-ray Absorption Fine Structure) regions of the excited state complex are detected. The XANES line shapes have been quantitatively simulated using a crystal field multiplet code in trigonal symmetry. In addition, spectral changes in the EXAFS region of both ground and excited states are analyzed in order to extract structural parameters of their corresponding molecular structures. We obtain a Ru-N bond contraction by approximately 0.03 angstroms in the excited-state complex, as compared to the ground-state compound. This contraction results from electrostatic and polarization contributions, limited by steric constraints on the bpy ligands.     

An explicit formula for the linearization coefficients of Bessel polynomials

We prove a single sum formula for the linearization coefficients of the Bessel polynomials. In two special cases we show that our formula reduces indeed to Berg and Vignat??s formulas in their proof of the positivity results about these coefficients (Constr. Approx. 27:15?C32, 2008). As a bonus we also obtain a generalization of an integral formula of Boros and Moll (J. Comput. Appl. Math. 106:361?C368, 1999).     

Robust stability of uncertain piecewise-linear systems: LMI?approach

In this paper we propose sufficient conditions for the robust stability of time-invariant uncertain piecewise-linear systems using homogeneous polynomial Lyapunov functions. The proposed conditions are expressed in terms of linear matrix inequalities, which can be numerically determined. We solve the stabilization of piecewise uncertain linear control systems by using state piecewise-linear feedback. We propose an illustrative example to show the efficiency of the proposed approach.     

The nanocellulose biorefinery: woody versus herbaceous agricultural wastes for NCC production

In the present work two agricultural residues (apple tree pruning and pea stalks) were studied as sources of nanocellulose. Different pretreatments that might be used in a biorefinery were applied to these lignocellulosic materials: autohydrolysis, organosolv (acetosolv) and alkaline pretreatments. After conventional bleaching, the resulting cellulosic fractions were submitted to a classical acid hydrolysis for nanocellulose crystal (NCC) production. The results showed that after applying different pretreatments, the resulting NCCs had different lengths (from 300 to 676 nm), surface charges (from 17 to 98 μmol acid groups/g NCC), purity (from 0.3 to 11.6% w/w of inorganics), crystallinity indexes and even allomorphism. These results highlighted the importance that cellulose source and particularly the applied pretreatments have on nanocrystal properties and suggest how biorefining pathways for lignocellulosic materials could customize such NCC features as surface reactivity or suitability for chemical modification.     

Ultrafast excited-state dynamics of rhenium(I) photosensitizers [Re(Cl)(CO)3(N,N)] and [Re(imidazole)(CO)3(N,N)]+: diimine effects

Femto- to picosecond excited-state dynamics of the complexes [Re(L)(CO)(3)(N,N)](n) (N,N = bpy, phen, 4,7-dimethyl-phen (dmp); L = Cl, n = 0; L = imidazole, n = 1+) were investigated using fluorescence up-conversion, transient absorption in the 650-285 nm range (using broad-band UV probe pulses around 300 nm) and picosecond time-resolved IR (TRIR) spectroscopy in the region of CO stretching vibrations. Optically populated singlet charge-transfer (CT) state(s) undergo femtosecond intersystem crossing to at least two hot triplet states with a rate that is faster in Cl (～100 fs)(-1) than in imidazole (～150 fs)(-1) complexes but essentially independent of the N,N ligand. TRIR spectra indicate the presence of two long-lived triplet states that are populated simultaneously and equilibrate in a few picoseconds. The minor state accounts for less than 20% of the relaxed excited population. UV-vis transient spectra were assigned using open-shell time-dependent density functional theory calculations on the lowest triplet CT state. Visible excited-state absorption originates mostly from mixed L;N,N(?-) → Re(II) ligand-to-metal CT transitions. Excited bpy complexes show the characteristic sharp near-UV band (Cl, 373 nm; imH, 365 nm) due to two predominantly ππ*(bpy(?-)) transitions. For phen and dmp, the UV excited-state absorption occurs at ～305 nm, originating from a series of mixed ππ* and Re → CO;N,N(?-) MLCT transitions. UV-vis transient absorption features exhibit small intensity- and band-shape changes occurring with several lifetimes in the 1-5 ps range, while TRIR bands show small intensity changes (≤5 ps) and shifts (～1 and 6-10 ps) to higher wavenumbers. These spectral changes are attributable to convoluted electronic and vibrational relaxation steps and equilibration between the two lowest triplets. Still slower changes (≥15 ps), manifested mostly by the excited-state UV band, probably involve local-solvent restructuring. Implications of the observed excited-state behavior for the development and use of Re-based sensitizers and probes are discussed.     

Identification of internal cracks in a three-dimensional solid body via Steklov–Poincaré approaches

This Note deals with the identification of internal planar cracks inside a three-dimensional elastic body via two approaches relying on domain decomposition using elastostatic measurements. These approaches consist in recasting the problem in terms of primal or dual Steklov–Poincaré equations. The primal approach is a straightforward continuation to the elastic Cauchy problem of the work presented in J. Ben Abdallah (2007) [1] which is devoted to the Cauchy problem for the scalar Laplace equation. The numerical performances of these formulations are compared.     

Constitutive equations for fiber suspensions in viscoelastic media

The kinetic theory of elastic dumbells with a friction factor that depends on the fiber orientation is used to obtain constitutive equations for fiber suspensions in a polymer matrix. We followed the approach of Fan (X.J. Fan, in P. Moldenaers and R. Keunings (Eds.), Theoretical and Applied Rheology, Proceedings XIth International Congress on Rheology, Brussels, Elsevier, Amsterdam, 1992, pp. 850–852), and derived equations for polymer solutions based on the FENE-P, FENE-CR, and Giesekus models. Start-up and steady-state free shear flows are studied to explore the effects of the fiber-polymer coupling as well as the fiber volume fraction. Predictions based on different types of closure approximations for the fourth-order fiber orientation tensor are also discussed.