Diphosphine ligand chelation and bridging and regiospecific ortho metalation in the reaction of 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) with Ir4(CO)12: X-ray diffraction structures of Ir4(CO)7(μ-CO)3(bpcd), Ir4(CO)5(μ-CO)3(bpcd)(μ-bpcd), and HIr4(CO)4(μ-CO)3(bpcd)[μ-PhP(C6H4)CC(PPh2)C(O)CH2C(O)]

Me₃NO activation of the tetrairidium cluster Ir₄(CO)₁₂ (1) in presence of the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) furnishes the bpcd-substituted clusters Ir₄(CO)₁₀(bpcd) (3) and Ir₄(CO)₈(bpcd)₂ (4) as the minor and major products, respectively. Cluster 3 has been isolated as the sole observable product from the reaction of [Ir₄(CO)₁₁Br][Et₄N] (2) with bpcd in presence of AgBF₄ at room temperature. Both 3 and 4 have been isolated and fully characterized in solution by spectroscopic methods. The solid-state structure of 3 reveals that the ancillary bpcd ligand is bound to a single iridium center, with chelating and bridging bpcd ligands found in the X-ray structure of cluster 4. Cluster 4 is unstable at room temperature and slowly loses CO to afford the hydride-bridged cluster HIr₄(CO)₄(μ-CO)₃(bpcd)[μ-PhP(C₆H₄)CC(PPh₂)C(O)CH₂C(O)] (5). Cluster 5 has been fully characterized in solution by IR and NMR spectroscopies, and the C–H bond activation attendant in the ortho metalation step is shown to occur regioselectively at one of the aryl groups associated with the bridging bpcd ligand. The redox properties of clusters 3–5 have been explored and the electrochemical behavior discussed with respect to extended Hückel MO calculations and related diphosphine-substituted cluster compounds prepared by our groups.     

Nonlinear vibrational spectroscopic studies of the adsorption and speciation of nitric acid at the vapor/acid solution interface

Nitric acid plays an important role in the heterogeneous chemistry of the atmosphere. Reactions involving HNO(3) at aqueous interfaces in the stratosphere and troposphere depend on the state of nitric acid at these surfaces. The vapor/liquid interface of HNO(3)-H2O binary solutions and HNO(3)-H(2)SO(4)-H2O ternary solutions are examined here using vibrational sum frequency spectroscopy (VSFS). Spectra of the NO2 group at different HNO(3) mole fractions and under different polarization combinations are used to develop a detailed picture of these atmospherically important systems. Consistent with surface tension and spectroscopic measurements from other laboratories, molecular nitric acid is identified at the surface of concentrated solutions. However, the data here reveal the adsorption of two different hydrogen-bonded species of undissociated HNO(3) in the interfacial region that differ in their degree of solvation of the nitro group. The adsorption of these undissociated nitric acid species is shown to be sensitive to the H2O:HNO(3) ratio as well as to the concentration of sulfuric acid.     

The interaction of EDTA with barium sulfate

Ethylenediaminetetraacetic acid (EDTA) is a known complexing agent that interacts with a host of cations. In this paper, various techniques are used to elucidate the mechanism of interaction between EDTA and barium sulfate surfaces. It is shown that complexation with metal ions is not sufficient to explain the inhibition of barite crystallization but that other processes such as chemisorption must also occur. EDTA is shown to always adsorb as the mono-protonated species - suggesting that the molecule is able to lose a proton when it adsorbs at lower pH. Molecular modelling shows that the interaction of the surface barium ions with the carboxylate group is an important one. Finally, in situ turbidity measurements provide information about the mechanism of nucleation/growth modification. It is found that the EDTA molecule inhibits barium sulfate nucleation and that this could be its primary means of inhibiting precipitation of barium sulfate.     

Correlation of Moments and Critical Phenomenon in Disassembly of Hot Nuclei

We used Monte Carlo method to generate the configurations of disassembly of hot nucleus Au* based on the Atomic Mass Table and the conservation of mass and charge number.The resulted charge distribution of fragments was then used to calculate the conditional moments.The logarithm correlation between second and third moments of experimental charge distribution is very well reproduced by theory.It seems that no connection to the critical phenomenon of concerned system exists.     

THE EFFECT OF THE FREEZE-OUT VOLUME IN THE MULTIFRAGMENTATION OF VERY HOT NUCLEAR REMNANT

In this paper a simplified method for the calculation of average Coulomb energy in statistical model of the disassembly processes of hot nuclei is proposed.The effect of freeze-out volume is studied based on the assumption of Gaussion-like distribution.It is indecated that the centre and dispersion of Gaussion-like distribution somewhat reflect the location and the renge of liquid-gas coexistence phase.     

Search for a bound trineutron with the 3He(π−pgr;+)nnn reaction

A search for the production of a bound trineutron state has been performed using the reaction ³He(π⁻,π⁺)nnn at incident pion energies of 65, 75, and 120 MeV. No evidence for the existence of the ³n was found, and an upper limit for the production cross section of approximately 30 nb/sr (2σ confidence level) was obtained. Received: 22 October 1998     

Optical fibre beam delivery of high-energy laser pulses: beam quality preservation and fibre end-preparation

This paper investigates the extension of optical fibre beam delivery to high-brightness applications, in particular laser percussion drilling, where both a good beam quality and high peak power are required. Beam quality preservation through a number of optical fibres is studied both experimentally and by using a ray propagation model. It is determined that in order to achieve the beam quality required for percussion drilling (M²<30) the largest fibre which can be used is 400 μm diameter. The laser-induced damage threshold is measured for a number of 400 μm fibres, and a CO₂ laser-annealing technique is shown to increase the damage threshold by a factor of 10, allowing 28 J, 1 ms pulses to be transmitted.     

200A GeV S+Au反应中光子产生的低横动量增强

用建立在LUND弦模型特别是PYTHIA事件产生器基础上的描写极端相对论性核-核碰撞的强子和弦级联模型--JPCIAE研究了入射能量为200A GeV的S+Au中心碰撞中光子产生.模型同时考虑了部分子QCD散射过程、强子末态相互作用以及强子衰变等光子产生反应道并作了协调处理.JPCIAE模型计算结果很好再现了WA93实验数据所呈现的低横动量增强效应.     

Synthesis and characterisation of lamellar ZnS nanosheets containing intercalated diamines

A solvothermal method has been used to prepare hybrid inorganic–organic composites with a lamellar structure in which layers of wurtzite ZnS are separated by intercalated diamine molecules. A hybrid composite prepared with diethylenetriamine has been isolated and characterised and its structure and properties compared with those of the composite prepared using ethylenediamine. Comparative structural and morphological studies of the two lamellar hybrid composites are described on the basis of powder XRD, electron and scanning probe microscopies and thermal analysis of the materials.     

Adsorption and reaction of CO2 and SO2 at a water surface

The orientation and hydrogen bonding of water molecules in the vapor/water interfacial region in the presence of SO2 and CO2 gas are examined using vibrational sum-frequency spectroscopy (VSFS) to gain insight into the adsorption and reactions of these gases in atmospheric aerosols. The results show that an SO2 surface complex forms when the water surface is exposed to an atmosphere of SO2 gas. Reaction of SO2 with interfacial water leads to other spectral changes that are examined by studying the VSF spectra and surface tension isotherms of several salts added to the aqueous phase, specifically NaHSO3, NaHCO3, Na2SO3, Na2CO3, Na2SO4, and NaHSO4. The results are compared with similar studies of CO2 adsorption and reaction at the surface. A weakly bound surface complex is not observed with CO2.