Studies of the compositions of Pd(II) hydrolysis products

The characterization of the clusters formed on alkaline hydrolysis of [PdCl₄]^2– was performed using¹⁷O,²³Na,³⁵Cl,¹³³Cs NMR and UV spectroscopy. The chemical composition of the clusters was found to be [Pd(OH)₂] _n ·nNaCl. No mononuclear oxo- or hydroxocomplexes were detected. The spatial structure of the clusters is stabilized by alkali metal cations.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 675–679, April, 1993.     

The Lamb-dip spectrum of methylcyanide: Precise rotational transition frequencies and improved ground-state rotational parameters

Methylcyanide, CH₃CN, is an important interstellar species, and therefore the accurate knowledge of precise rest frequencies for rotational transitions as well as ground-state rotational and hyperfine constants is needed. In this work the hyperfine structure of the millimeter- and submillimeter-wave spectra of CH₃CN has been further investigated. In addition, accurate THz measurements have been carried out for the first time. Consequently, the present investigation allowed us to provide the most accurate ground state rotational and hyperfine parameters known at the moment for CH₃C¹⁴N. To resolve the hyperfine structure of the rotational transitions observed, the Lamb-dip technique has been exploited. Both frequency-modulated and video-type detections have been employed.     

High pressure X-ray diffraction study of CdAl2Se4 and Raman study of AAl2Se4 (A=Hg, Zn) and CdAl2X4 (X=Se, S)

We report the results of an X-ray diffraction study of CdAl₂Se₄ and of Raman studies of HgAl₂Se₄ and ZnAl₂Se₄ at room temperature, and of CdAl₂S₄ and CdAl₂Se₄ at 80 K at high pressure. The ambient pressure phase of CdAl₂Se₄ is stable up to a pressure of 9.1 GPa above which a phase transition to a disordered rock salt phase is observed. A fit of the volume pressure data to a Birch-Murnaghan type equation of state yields a bulk modulus of 52.1 GPa. The relative volume change at the phase transition at ∼9 GPa is about 10%. The analysis of the Raman data of HgAl₂Se₄ and ZnAl₂Se₄ reveals a general trend observed for different defect chalcopyrite materials. The line widths of the Raman peaks change at intermediate pressures between 4 and 6 GPa as an indication of the pressure induced two stage order-disorder transition observed in these materials. In addition, we include results of a low temperature Raman study of CdAl₂S₄ and CdAl₂Se₄, which shows a very weak temperature dependence of the Raman-active phonon modes.     

复合体系方法测量液体力学谱

本文介绍了采用复合体系，测量得到凝聚态物质从固态到液态连续变化力学谱的一种新的实验方法。以簧振动为例，给出了解析的计算公式，以及应用条件。通过进一步综合分析，得到具有更广应用范围的近似公式，可以近似应用于其他不同的振动模式，如低频扭摆。应用新的测量方法，给出了典型小分子玻璃材料甘油和碳酸丙稀从玻璃态到液态的力学谱，观察到甘油和碳酸丙稀玻璃化转变、碳酸丙稀的再结晶、熔化和挥发的过程；测量得到挥发过程中水的质量随时间精确变化的曲线。最后，本文给出了新方法的一些应用展望。     

Quantum chaos and fractals with atoms in cavities

We study the coupled translational, electronic, and field dynamics of the combined system “a two-level atom + a single-mode quantized field + a standing-wave ideal cavity”. In the semiclassical approximation with a point-like atom, interacting with the classical field, the dynamics is described by the Heisenberg equations for the atomic and field expectation values which are known to produce semiclassical chaos under appropriate conditions. We derive Hamilton–Schrödinger equations for probability amplitudes and averaged position and momentum of a point-like atom interacting with the quantized field in a standing-wave cavity. They constitute, in general, an infinite-dimensional set of equations with an infinite number of integrals of motion which may be reduced to a dynamical system with four degrees of freedom if the quantized field is supposed to be initially prepared in a Fock state. This system is found to produce semiquantum chaos with positive values of the maximal Lyapunov exponent. At exact resonance, the semiquantum dynamics is regular. At large values of detuning |δ|1, the Rabi atomic oscillations are usually shallow, and the dynamics is found to be almost regular. The Doppler–Rabi resonance, deep Rabi oscillations that may occur at any large value of |δ| to be equal to |αp₀|, is found numerically and described analytically (with α to be the normalized recoil frequency and p₀ the initial atomic momentum). Two gedanken experiments are proposed to detect manifestations of semiquantum chaos in real experiments. It is shown that in the chaotic regime values of the population inversion z_out, measured with atoms after transversing a cavity, are so sensitive to small changes in the initial inversion z_in that the probability of detecting any value of z_out in the admissible interval [−1,1] becomes almost unity in a short time. Chaotic wandering of a two-level atom in a quantized Fock field is shown to be fractal. Fractal-like structures, typical with chaotic scattering, are numerically found in the dependence of the time of exit of atoms from the cavity on their initial momenta.     

An AFM, XPS and electrochemical study of molecular electroactive monolayers formed by wet chemistry functionalization of H-terminated Si(1 0 0) with vinylferrocene

Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η⁵-C₅H₅)Fe²⁺(η⁵-C₅H₄)-CH₂-CH₂-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe³⁺ at the expenses of Fe²⁺ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO⁻ groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe³⁺ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing.     

FT-IR study on solvent effects in building blocks of bioactive compounds. V

3-Hydroxy-4-hydroxymethyl pyrrolidin-2-ones, easily prepared from the Baylis–Hillman adduct 1-ethyl-4-methyl-2-hydroxy-3-methylenebutanedioate, are useful intermediates in the synthesis of bioactive compounds. In order to understand the mechanism involved in this reaction, vibrational and Montecarlo molecular mechanics conformational analysis on 1-ethyl-4-methyl-2-hydroxy-3-methylenebutanedioate were carried out, confirming the existence of a low energy intramolecular H-bonded five-member ring.     

Electronic transport properties of bismuth nanobridges through silicon-nitride membranes

The electronic transport through nanostructured bismuth nanobridges has been investigated at low temperatures (T<2 K) and in magnetic fields B up to 8.5 T. The samples show reproducible resistance fluctuations as a function of B, superimposed on a large magnetoresistance of up to 50%. In addition, time-dependent resistance fluctuations in zero magnetic field demonstrate the presence of bistable scatterers in the constriction region of our samples, which are described by two-level systems. Their dynamics are shown to be sensitive to subtle modifications of the static scatterer configuration in their vicinity, which cannot be detected in the sample magnetofingerprint.     

Radiative lifetimes in Ce I and Ce II

New radiative lifetime measurements based on time-resolved laser-induced fluorescence techniques are reported for 18 even-parity levels belonging to the 4f5d^26p and 4f ²5d ² configurations of Ce I and 6 even-parity levels belonging to the 5d^26s, 4f5d6p, and 4f6s6p configurations of Ce II. Free neutral and singly ionized cerium atoms were produced by laser ablation. The Ce I and Ce II levels range in energy from 26 545 to 29 102 cm^-1, and 42 573 to 48 152 cm^-1, respectively. Received 25 September 2002 Published online 4 March 2003     

What Oxidation State of Iron Determines the Amethyst Colour?

A colourless quartz crystal doped with ⁵⁷Fe³⁺ was obtained by hydrothermal synthesis in an NH₄F solution. The crystal was transformed into violet amethyst by gamma-irradiation. The change in colour was accompanied by changes in the Mössbauer spectrum that can be interpreted as the conversion of trivalent iron into the tetravalent state: Fe³⁺→Fe⁴⁺.