Spatiotemporal mapping of surface acoustic waves in isotropic and anisotropic materials

We demonstrate a new method for a real-time imaging of surface acoustic waves at frequencies up to 1 GHz with picosecond temporal and micron spatial resolutions using an ultrafast optical pump and probe technique combined with a common path interferometer. Using samples with isotropic or anisotropic substrates coated with metallic thin films, we observe the propagation of Rayleigh-like modes and surface-skimming bulk modes as well as resolving surface phonon focusing effects. In addition we image surface acoustic wave propagation in a laterally inhomogeneous sample.     

Rotational bands and signature inversion phenomena in πh9/2⊗νi13/2 and πi13/2⊗νi13/2 structures in odd-odd 176Ir

The ^109,111,113Rh nuclei have been produced as fission fragments in the fusion reaction ¹⁸O + ²⁰⁸Pb at 85 MeV. Their level schemes have been built from gamma-rays detected using the Euroball IV array. High-spin states of the neutron-rich ^111,113Rh nuclei have been identified for the first time. Several rotational bands with the odd proton occupying the πg _9/2, πp _1/2 and π(g _7/2/d _5/2) sub-shells have been observed. A band of low-energy transitions has been identified at excitation energy around 2 MeV in ^109,111Rh, which can be interpreted in terms of three-quasiparticle excitation, πg _9/2νh _11/2νg _7/2/d _5/2. In addition another structure built on states located at low excitation energy (608 keV in ¹¹¹Rh, 570 keV in ¹¹³Rh) points out that, as already observed in the lighter isotopes ^107,109Rh, triaxial deformation plays a role in the neutron-rich Rh isotopes well beyond the mid-shell. Received: 15 July 2002 / Accepted: 9 October 2002 / Published online: 3 December 2002 RID="a" ID="a"e-mail: porquet@csnsm.in2p3.fr RID="b" ID="b"Present address: CSNSM IN2P3-CNRS and Université Paris-Sud 91405 Orsay, France. RID="c" ID="c"Present address: CEA/Saclay, DSM/DAPNIA/SPhN, 91191 Gif-sur-Yvette Cedex, France. Communicated by D. Schwalm     

形变双奇核178Ir转动带能级的旋称反转

利用¹⁵²Sm(³¹P,5nγ)¹⁷⁸Ir反应产生并研究了双奇核¹⁷⁸Ir的高自旋态.实验中进行了¹⁷⁸Ir核的在束γ测量,包括γ射线的激发函数测量、X–γ和γ–γ符合测量.首次建立了双奇核¹⁷⁸Ir基于πh_9/2νi_13/2和πh_11/2νi_13/2准粒子组态上的转动带能级纲图.发现在低自旋区,两个转动带能级均出现旋称反转.对此核区半退耦带的旋称反转作了简要的分析和讨论.     

Asymmetric Total Synthesis of Indole Alkaloids Containing an Indoline Spiroaminal Framework

The total synthesis of the indole alkaloids, neoxaline, oxaline and meleagrin A, all containing a unique indoline spiroaminal framework, was accomplished through the stereoselective introduction of a reverse prenyl group to the congested benzylic carbon of furoindoline, a two‐pot transformation of indoline (containing three nitrogen atoms at appropriate positions) to the featured indoline spiroaminal framework, and elimination of carbonate assisted by the adjacent imidazole moiety to construct the (E)‐dehydrohistidine. The absolute stereochemistry of neoxaline was elucidated through our total synthesis. In addition, we evaluated the bioactivity, especially the anti‐infectious properties, of neoxaline and oxaline, and of some synthetic intermediates.     

Quantum tautomerization in porphycene and its isotopomers: Path-integral molecular dynamics simulations

Path-integral molecular dynamics simulations have been performed for porphycene and its isotopic variants in order to understand the effect of isotopic substitution of inner protons on the double proton transfer mechanism. We have used an on-the-fly direct dynamics technique at the semiempirical PM6 level combined with specific reaction parameterization. Our quantum simulations show that double proton transfer of the unsubstituted porphycene at T = 300 K mainly occurs via a so-called concerted mechanism through the D_2h second-order saddle point. In addition, we found that both isotopic substitution and temperature significantly affect the double proton transfer mechanism. For example, the contribution of the stepwise mechanism increases with a temperature increase. We have also carried out hypothetical simulations with the porphycene configurations being completely planar. It has been found that out-of-plane vibrational motions significantly decrease the contribution of the concerted proton transfer mechanism.     

Trigonally-compressed octahedral geometry of hexaamminecobalt(III) complex cation in aqueous solution investigated from the electronic spectra

Electronic spectra of hexaamminecobalt(III) complex cation in aqueous solution were analyzed to obtain spectral components. Subsequently, based on the spectral components, the coordination geometry around the cobalt(III) ion was investigated, using the reverse angular overlap model method. The result indicates that the geometry is a trigonally compressed octahedron with the polar angle of 57.9?±?1.0° under D_3d symmetry, where the polar angle is the angle between the trigonal axis and the Co–N bond. From this angle, the top and side N–Co–N bond angles are calculated as 94.4° and 85.6°, respectively. The density functional theory computation supported this trigonally compressed structure in aqueous solution.     

Effect of the melting system sizes on the temperature and concentration combined melting of a vertical ice plate in a rectangular cavity

This paper is concerned with the melting of a vertical ice plate into a calcium chloride aqueous solution inside a rectangular cavity. The initial temperature of the ice plate and the mixture are both −5°C and the initial concentration of the mixture is 20 wt%. The effect of the liquid height H, the width W, the aspect ratio of the liquid region A (=H/W) and the initial ice plate thickness δ _i on the transient melting mass per unit melting front area, M, is mainly considered numerically. M keeps a similar value in spite of H varied for A = 1 at early melting stage, however, becomes considerably influenced by H as melting progresses. The ice plate melts influenced by A for H = 20 mm fixed at early melting stage due to the fast development of the stagnant region and M decreases with increasing A (=1∼ 10). A dimensionless correlation of the transient melting mass, the aspect ratio and the melting time was presented under the restricted condition of H = 20 mm.     

Switching of Redox Properties Triggered by a Thermal Equilibrium between Closed‐Shell Folded and Open‐Shell Twisted Species

Thermally switchable redox properties have been reported to be due to a change in the spin state of newly designed overcrowded ethylenes, which can adopt closed‐shell folded and open‐shell twisted forms. In this study, tetrathienylanthraquinodimethane derivatives were designed to be in thermal equilibrium between a more stable folded form and less stable but more donating twisted diradical in solution, so that the oxidation potential can be controlled by heating/cooling. This is the first example of a switching of redox properties based on a thermally equilibrated twisted diradical, which can be more readily oxidized to the twisted dication.     

A Concise Route to 3-Hydroxy-4-Methoxy-5-Methylbenzaldehyde Derivative

3-Hydroxy-4-methoxy-5-methylbenzaldehyde derivative (1c) has been synthesized in 7 steps from 2,3-dihydroxytoluene (4). An isopropyl derivative has been used to protect a phenol during this transformation. The overall yield of 1c was 37%.