Coherent Vibration and Femtosecond Dynamics of the Platinum Complex Oligomers upon Intermolecular Bond Formation in the Excited State

Femtosecond time-resolved absorption and picosecond time-resolved emission measurements were carried out for highly concentrated aqueous solutions of K₂[Pt(CN)₄] to investigate excited-state dynamics of the [Pt(CN)₄²⁻] oligomers formed with metallophilic interactions. Time-resolved absorption spectra exhibit complicated dynamics that are represented with five time constants. Among them, the 90-ps and 400-ps dynamics were assigned to the S₁ → T₁ intersystem crossing of the trimer and tetramer coexisting in the solution by comparison with the fluorescence decays. Clear oscillations of transient absorption were observed in the first few picoseconds, and the frequency-detected-wavelength 2D analysis revealed that the 135-cm⁻¹ and 65-cm⁻¹ oscillations arise from the Pt–Pt stretch motions of the S₁ trimer and S₁ tetramer, respectively. The obtained time-resolved spectroscopic data provide a clear view of the excited-state dynamics of the [Pt(CN)₄²⁻] oligomers in the femto-/picosecond time region.     

Transient bonds and chemical reactivity of molecules

Electron delocalization between the reagent and reactant molecules is the principal driving force of chemical reactions. It brings about the formation of new bonds and the cleavage of old bonds. By taking the aromatic substitution reaction as an example, we have shown the orbitals participating in electron delocalization. The interacting orbitals obtained are localized around the reaction sites, showing the chemical bonds that should be generated and broken transiently along the reaction path. By projecting a reference orbital function that has been chosen to specify the bond being formed on to the MOs of the reactant molecules, the reactive orbitals that are very similar to the interacting orbital have been obtained. The local potential of the reaction site for electron donation estimated for substituted benzene molecules by using these projected orbitals shows a fair correlation with the experimental scale of the electron-donating and -withdrawing strength of substituent groups. The reactivity is shown to be governed by local electronegativity and local chemical hardness and also by the localizability of interaction on the reaction site. © 1996 John Wiley & Sons, Inc.     

Time operators for quantum walks

Letters in Mathematical Physics - We study time operators for discrete-time quantum systems. Quantum walks are typical examples. We construct time operators for one-dimensional homogeneous quantum...     

碳酸二甲酯法合成1,5-萘二氨基甲酸甲酯的反应机理

 应用红外光谱技术研究了在乙酸锌催化作用下1,5-萘二胺与碳酸二甲酯甲氧基羰基化反应机理. 结果表明,二水合乙酸锌只有失去两个结晶水变成无水乙酸锌后才能产生催化活性. 无水乙酸锌与1,5-萘二胺形成一个新的配位络合物,该配位络合物是一个适宜的亲核试剂,能与碳酸二甲酯进行亲核反应,生成1,5-萘二胺的甲氧基羰基化产物. 在无水乙酸锌与1,5-萘二胺形成配位络合物的过程中,无水乙酸锌的结构从双齿型转变成单齿型.     

Scalable Total Syntheses and Structure–Activity Relationships of Haouamines A,B, and Their Derivatives as Stable Formate Salts

Haouamines A, B, and their derivatives were synthesized via Suzuki–Miyaura coupling and three key cyclization reactions as follows: the newly developed palladium(0)-catalyzed arylative cyclization of phenylalanine-derived alkyne–aldehydes with 2-bromoarylboronic acid (an “anti-Wacker”-type cyclization); BF₃ ⋅ OEt₂-promoted Friedel–Crafts-type cyclization of symmetrical electron-rich aromatic rings adjacent to a tertiary allylic alcohol leading to the indeno-tetrahydropyridine skeleton; and (cyanomethyl)trimethylphosphonium iodide-mediated macrocyclization of amino alcohols to afford aza-paracyclophane precursors. The palladium-catalyzed reduction of mono- and di-triflate intermediates in the later stages enabled the alteration of both the position and number of hydroxyl groups on the C-ring. The instability of haouamine B was dramatically improved by salt formation with formic acid. An unambiguous evaluation of the cytotoxicity of the prepared haouamine derivative formates with and without hydroxyl groups at different positions on the C-ring indicated that the catechol structure in haouamine B produced weak cytotoxicity.     

Nonlinear mixing of oppositely travelling surface plasmons

A theoretical treatment of the nonlinear mixing of two contra-directional surface plasmons of frequency ω₁ and ω₂ propagating on a semi-infinite metal surface is presented. The nonlinear interaction is analysed in terms of (a) nonlinear surface currents due to the breaking of inversion symmetry and the rapid variation of the normal electric field component at the surface, and (b) the nonlinear response of the electron gas in the bulk of the metal. These currents are treated as source terms for Maxwell's equations and electromagnetic fields are found which satisfy the driven wave equation and boundary conditions at the frequencies ω₁ ± ω₂. At the difference frequency ω₁ ? ω₂ the solution fields decay exponentially into both the air and the metal. However, at the sum frequency ω₁ + ω₂, coupling to transverse electromagnetic waves in both the air and the metal is predicted under appropriate wavevector and frequency conditions. The free-space radiation field is treated in detail and the feasibility of its experimental detection is discussed. No coupling to longitudinal bulk plasmons is predicted in this model of the nonlinear interaction.     

High-pressure and high-temperature generation using diamond/sic composite anvils prepared with hot isostatic pressing

Using a hot isostatic pressing (HIP) technique, we synthesized diamond/SiC composites from diamond and Si powders. At an HIP condition of 1450 °C and 100 MPa, a pressure much lower than that of the diamond stability field, diamond powders react with molten Si to form well-sintered diamond/SiC composites. Cubes of the composites with 15 mm edge length were thereby fabricated, and an application to the second stage anvils in a Kawai-type high-pressure apparatus was attempted. A hybrid anvils system using four cubes of the composites and four of the conventional WC was introduced and heating experiments up to 1600 °C became possible. Because the diamond/SiC composites are transparent to X-rays, the present system is applicable not only to diffraction studies but also to radiographic studies that need a larger window for an X-ray image.     

A Low-Noise 230 GHz SIS Receiver for Radio Astronomy Employing Untuned Nb/AlOx/Nb Tunnel Junctions

A heterodyne receiver based on a 1/3 reduced height rectangular waveguide SIS mixer with two mechanical tuners has been built for astronomical observations of molecular transitions in the 230 GHz frequency band. The mixer used an untuned array (R_nC_j3, R_n70 ) of four Nb/AIOx/Nb tunnel junctions in series as a nonlinear mixing element. A reasonable balance between the input and output coupling efficiencies has been obtained by choosing the junction number N=4. The receiver exhibits DSB (Double Side Band) noise temperature around 50 K over a frequency range of more than 10 GHz centered at 230 GHz. The lowest system noise temperature of 38 K has been recorded at 232.5 GHz. Mainly by adjusting the subwaveguide backshort, the SSB (Single Side Band) operation with image rejection of 15 dB is obtained with the noise temperature as low as 50 K. In addition, the noise contribution from each receiver component has been studied further. The minimum SIS mixer noise temperature is estimated as 15 K, pretty close to the quantum limit v/k11 K at 230 GHz. It is believed that the receiver noise temperatures presented are the lowest yet reported for a 230 GHz receiver using untuned junctions.     

Lax表示的变形与Hamilton方程族的Lax表示

本文首先给出了构造演化方程族的Ｌａｘ表示的马文秀方法的一种变形，后对这一方法作了改进，使之适用于Ｈａｍｉｌｔｏｎ形式的方程族．作为应用，得到了具有非等谱Ｌａｘ表示的杨方程族．     

Plasma production by helicon and slow waves

The observation of slow-wave sustained (SW) discharge in a whistler- or helicon-wave range of frequency is made using high-frequency and very-high-frequency bands of rf. The SW discharge occurs at an extremely low rf power and plasma density, which are lower than a capacitive-coupling discharge region.