Intramolecular Anion Effect in Polyoxometalate‐Based Organocatalysts: Reactivity Enhancement and Chirality Transfer by a Metal Oxide–Organic Cation Interaction

An α₁‐Dawson polyanion bearing a lateral side chain with a 4‐aminopyridine end group was synthesized. This organopolyoxometalate catalyzes the addition of indenyl allyl silanes to cinnamoyl fluorides. The polyanionic framework influences the organocatalyst activity and selectivity. A moderate but nonzero chirality transfer from the chiral inorganic framework to the organic substrate was observed.     

Application of polarized neutron reflectometry and X-ray resonant magnetic reflectometry for determining the inhomogeneous magnetic structure in Fe/Gd multilayers

The evolution of the magnetic structure of multilayer [Fe (35 Å)/Gd (50 Å)₅] with variation in temperature and an applied magnetic field was determined using a complementary approach combining polarized neutron and X-ray resonant magnetic reflectometry. Self-consistent simultaneous analysis of X-ray and neutron spectra allowed us to determine the elemental and depth profiles in the multilayer structure with unprecedented accuracy, including the identification of an inhomogeneous intralayer magnetic structure with near-atomic resolution.     

Spectroscopy of XY3Z (C3v) molecules: A tensorial formalism adapted to the O (3) ⊃ C∞v ⊃ C3v group chain

A tensorial formalism adapted to the case of XY₃Z symmetric tops has been developed. We use the O (3) ⊃ C_∞v ⊃ C_3v group chain. All the coupling coefficients and formulas for the computation of the matrix elements are given for this chain. Such relations are also deduced in C_3v group itself.     

Tuning and stability of a continuous-wave mid-infrared high-power single resonant optical parametric oscillator

A 2.2-W continuous-wave, continuously tunable, single-frequency OPO has been developed in the 3.0–3.8 μm wavelength range for the detection of molecular trace gasses. The oscillation threshold, output power and stability of the single resonant OPO were improved by optimizing pump beam waist and OPO cavity length. Both air-spaced and solid etalons were tested to frequency stabilize and tune the OPO, from which the solid etalon gave a better performance. Temperature oscillations in the PPLN crystal caused oscillations in the idler wavelength of less than 200 MHz over 300 s; the short-term stability was less than 3 MHz over 1 s. The high laser power, in combination with photoacoustic spectroscopy, achieved a detection limit of 10 parts-per-trillion for ethane in nitrogen. Received: 9 April 2002 / Revised version: 14 June 2002 / Published online: 2 September 2002 RID="*" ID="*"Corresponding author. Fax:+31-24/3653311, E-Mail: maartenh@sci.kun.nl     

Experimental study of AO and T1 modes of the concert harp

String instruments are usually composed of a set of strings, a soundboard, and a soundbox with sound holes, which is generally designed to increase the sound level by using the acoustic resonances of the cavity. In the case of the harp, the soundbox and especially the sound holes are primarily designed to allow access to the strings for their mounting. An experimental modal analysis, associated to measurements of the acoustic velocity in the holes, shows the importance of two particular modes labeled A0 and T1 as it was done for the guitar and the violin. Their mode shapes involve coupled motions of the soundboard's bending and of the oscillations of the air pistons located in the sound holes. The A0 mode is found above the frequency of the lowest acoustically significant structural mode T1. Thus, the instrument does not really take advantage of the soundbox resonance to increase its radiated sound in low frequencies. However, contribution of mode A0 is clearly visible in the response of the instrument, confirming the importance of the coupling between the soundboard and the cavity.     

O(n) tricriticality in two dimensions

We present exact results for several universal parameters of the tricritical O(n) model in two dimensions. The results apply to the range −2⩽n⩽3/2, and include the central charge and three scaling dimensions, associated with temperature, magnetic field and the introduction of an interface. Since these results are based on an extrapolation of known relations between the O(n) and the Potts model, they cannot be considered as rigorous. For this reason, we perform an accurate numerical analysis of the central charge and the critical exponents. This analysis, which is based on transfer-matrix calculations on the honeycomb lattice, is in a full and precise agreement with the theoretical predictions.      

Assessment of several hybrid DFT functionals for the evaluation of bond length alternation of increasingly long oligomers

We have optimized the ground-state geometry of nine series of increasingly long oligomers, using six hybrid density functionals (O3LYP, B3LYP, B97-1, B98, PBE0, and BHHLYP) combined with three different atomic basis sets. In each case, the obtained bond length alternation (BLA) is compared to the corresponding MP2 values. Three phenomenological categories have been set up. In the first, the BLA exponentially decreases, in which case all the tested functionals give results in very good agreement with MP2. In the second category fall the symmetric oligomers that, due to the Peierls theorem, show large BLA. For these chains, BHHLYP tends to give too large and quickly converging BLA wrt chain length, while O3LYP often leads to the opposite misjudgments, and the remaining hybrids provide valuable results. In the third category, one finds asymmetric compounds presenting significantly unequal bond lengths, for which the divergence between DFT and wave function approaches can be dramatic. Indeed, all hybrids yield too small BLA values, especially for long chain lengths. We also study the effect of chain conformation on the BLA.