Fluorescence and intersystem crossing as a function of rotational energy on the S1 state of benzene

The effect of rotational excitation on the electronic relaxation of the S₁ state of “isolated” benzene has been studied by examination of resonance fluorescence generated when narrow-band exciting light is swept through the rotational envelopes of four S₁ ← S₀ absorption bands. To within the ten percent uncertainty in measurement, the fluorescence yields are independent of the position of the exciting light within an absorption band. Thus neither radiative decay nor intersystem crossing to the triplet state displays large sensitivity to molecular rotation, at least when excited state relaxation proceeds from rotational distributions of moderate diversity.     

Shock waves in nanomechanical resonators

We study the formation of shock waves in a nanomechanical resonator with an embedded two-dimensional electron gas using surface acoustic waves. The mechanical displacement of the nanoresonator is read out via the induced acoustoelectric current. Applying acoustical standing waves, we are able to determine the so-called anomalous acoustocurrent. This current is found only in the regime of shock wave formation.     

Methylalumoxane (MAO)-Derived MeMAO− Anions in Zirconocene-Based Polymerization Catalyst Systems – A UV-Vis Spectroscopic Study

Reaction of Me₂Si(Ind)₂ZrCl₂ with excess methylalumoxane (MAO) gives rise to ion pairs containing zirconocenium cations of the type [Me₂Si(Ind)₂ZrMe]⁺ in contact with two types of anions, MeMAO _A ⁻ and MeMAO _B ⁻, which differ in their coordinative strengths: More strongly coherent contact-ion pairs [Me₂Si(Ind)₂ ZrMe^+..MeMAO _B ⁻] are converted by a sufficiently high excess of MAO to more easily separable contact-ion pairs [Me₂Si(Ind)₂ZrMe^+..MeMAO _A ⁻], which react with AlMe₃ to form the outer-sphere ion pairs [Me₂Si(Ind)₂Zr(µ-Me)₂AlMe₂]⁺ MeMAO _A ⁻, and are likely to be required also for the formation of the olefin-containing reaction complexes responsible for catalytic activity.     

Zur struktur des diethylgermanium-diphenylsiliciumoxids und zur konformation von achtringen mit silicium und germanium

Diethylgermanium-diphenylsilicon oxide [(Et₂Ge)O(Ph₂Si)O]₂ has been prepared by reaction of diethylgermanium dichloride and diphenyldihydroxysilane. Spectra and X-ray analysis showed the presence of a puckered eight-membered silicon—germanium—oxygen ring. The ethyl groups of the germanium atoms are disordered. A procedure is proposed for eight-membered rings with low symmetry to obtain a classification into clearly explaining ring forms based on exact or approximated planes put through as many ring atoms as possible. All of the 42 published eight-membered rings with silicon or germanium and oxygen, nitrogen or carbon could be classified by this method.     

Hitting straight lines by compound Poisson process paths

In a recent article Mallows and Nair (1989,Ann. Inst. Statist. Math.,41, 1–8) determined the probability of intersectionP{X(t)=αt for somet≥0} between a compound Poisson process {X(t), t≥0} and a straight line through the origin. Using four different approaches (direct probabilistic, via differential equations and via Laplace transforms) we extend their results to obtain the probability of intersection between {X(t), t≥0} and arbitrary lines. Also, we display a relationship with the theory of Galton-Watson processes. Additional results concern the intersections with two (or more) parallel lines. Work done in part while these authors were visiting professors at the Indian Statistical Institute, Delhi Centre, New Delhi, 110016, India. This author's investigation was supported in part by the U. S. National Science Foundation Grant No. DMS-8504319. Our coauthor and friend Prem Singh Puri died on August 12, 1989. We dedicate our contribution to this paper to his memory.     

Observation of Ramsey fringes in nonlinear Faraday rotation

The evolution of Δm = 2 ground state coherences was investigated in a thermal Rb atomic beam using spatially separated laser beams. The coherence was created by optical pumping with a linearly polarized light beam and was probed, after evolving in a homogeneous magnetic field via the rotation of the plane of polarization of a second light beam. The observed signal shows dispersively shaped Ramsey fringes with a fringe width of 6 kHz.     

Accurate velocity reconstruction for Discontinuous Galerkin approximations of two-phase porous media flows

We consider Discontinuous Galerkin approximations of two-phase, immiscible porous media flows in the global pressure/fractional flow formulation with capillary pressure. A sequential approach is used with a backward Euler step for the saturation equation, equal-order interpolation for the pressure and the saturation, and without any limiters. An accurate total velocity field is recovered from the global pressure equation to be used in the saturation equation. Numerical experiments show the advantages of the proposed reconstruction. To cite this article: A. Ern et al., C. R. Acad. Sci. Paris, Ser. I 347 (2009).     

The role of dormant sites in propene polymerization using methylalumoxane activated metallocene catalysts

Propene polymerization of methylalumoxane (MAO) activated rac-Me₂Si(Benz[e]Indenyl)₂ZrCl₂ ( BI ) and rac-Me₂Si(2-Me-Benz[e]Indenyl)₂ZrCl₂ ( MBI ) was studied to investigate the influence of the ligand substitution pattern and the role of dormant sites. Poly(propene) end group composition as well as regio- and stereoirregularities were examined by means of ¹H- and ¹³C-NMR spectroscopy. Dormant sites, resulting from 2, 1-propene insertion, were reactivated either by β-hydrogen transfer to propene, yielding 2-butenyl end groups, or by 1, 2-insertion of propene, yielding regioirregularities. Propene polymerization in the presence of hydrogen gave n-butyl end groups and less regioirregularities as expected for hydrogenolysis of such dormant sites. Methyl substitution in 2-position of the benz[e]indenyl ligand suppressed β-hydrogen transfer to propene, and increased molecular weight with increasing propene concentration. Also, activation energy increased from 30 kJ/mol ( BI /MAO) to 59 kJ/mol ( MBI /MAO). For both catalysts activity depended on propene concentration. The order of reaction relative to propene was 1.7.