SiH2Cl2: ab initio anharmonic force field, dipole moments, and infrared vibrational transitions

The vibrational spectra of SiH2Cl2 have been recorded in the 1000-13,000 cm(-1) region, utilizing the Fourier-transform spectroscopy and Fourier-transform intracavity laser absorption spectroscopy. Totally 61 band centers and intensities are derived from the infrared spectra. An ab initio quartic force field is obtained by applying the second-order Moller-Plesset perturbation theory and correlation-consistent polarized valence triplet-zeta basis sets [J. Chem. Phys. 90, 1007 (1989); 98, 1358 (1993)]. Most observed bands are assigned by the vibration analysis based on the second-order perturbation theory. Reduced-dimensional ab initio dipole moment functions (two dimensional and three dimensional) have also been calculated to investigate the absolute band intensities of the SiH2 chromophore. The calculated values agree reasonably with the observed ones.     

Simultaneous ion-exclusion/cation-exchange chromatography of anions and cations in acid rain waters on a weakly acidic cation-exchange resin by elution with sulfosalicylic acid

A simple, selective, and sensitive method for the simultaneous determination of anions (sulfate, nitrate, and chloride) and cations (sodium, ammonium, potassium, magnesium, and calcium) in acid rain waters was developed using ion-exclusion/ cation-exchange chromatography with conductimetric detection. A weakly acidic cation-exchange resin column (Tosho TSKgel OA-PAK-A) and a sulfosalicylic acid-methanol-water eluent was used. With a mobile phase comprising 1.25 mM sulfosalicylic acid in methanol-water (7.5:92.5) at 1.2 ml/min, simultaneous separation and detection of the above anions and cations was achieved in about 30 min. Linear calibration plots of peak area versus concentration were obtained over the concentration ranges 0-1.0 mM for anions (R=0.9991) and 0-0.5 mM for cations (R=0.9994). Detection limits calculated at S/N=3 ranged from 4.2 to 14.8 ppb for the anions and from 2.4 to 12.1 ppb for the cations. The reproducibility of retention times was 0.14-0.15% relative standard deviation (RSD) for anions and 0.18-0.31% for cations, and reproducibility of chromatographic peak areas was 1.22-1.75% RSD for anions and 1.81-2.10% for cations. The method was applied successfully to the simultaneous determination of anions and cations in aerosols transported from mainland China to central Japan, as determined by a meteorological satellite data analyzer.     

Thermodynamics and dynamics of metallic glass formers: their correlation for the investigation on potential energy landscape

Great progress has been made in basic features of the potential energy landscape (PEL) theoretically. The present work, however, attempts to cast new light on it from experimental aspects. By a survey of experimental data related to thermodynamics or dynamics of metallic glass-forming liquids, it is found that the increased rate of excitation of vibrational entropy at glass transition tends to increase the rate of generation of configurational part. Although for the type of metallic materials a generally positive relationship exists between the density of the energy minima at glass transition and the liquid fragility strength, just as expected, our main attention is paid to the phenomenon of the scattering of the slopes. Analysis shows that the phenomenon results from the different average height of energy barriers between minima near glass transition. Investigation on the PdNiP metallic system indicates that the mismatch entropy is a dominant factor in the barrier height: a large value of it results in low energy barriers. Our previous work on the AlNiCe system gives the support to this finding.     

二芳基汞的合成

将氯化重氮苯的溶液加入氯化汞、维生素C、丙酮和少量氯化铜的混合物中,得到80％的氯化苯汞;如在反应混合物中补加维生素C、氯化铜和浓氨水,则得到二苯汞。用同样的方法制备了其他的二芳基汞,并讨论了反应可能的机理。     

Comparative studies of the photoinduced reactions in the Mg+-SCNC2H5 and Mg+-NCSC2H5 complexes

The photoinduced reactions of the complexes Mg+-SCNC2H5 and Mg+-NCSC2H5 are studied comparatively in the spectral range of 230-440 nm. One-photon excitation of the complexes through the Mg+ chromophore (3 2P <-- 3 2S) gives rise to the evaporative fragment as well as the molecular activation and charge transfer products. The action spectra of the complexes consist of three broad peaks for Mg+-SCNC2H5 and two for Mg+-NCSC2H5, which accord with the structures obtained from quantum mechanics calculations. These calculations reveal two association isomers for Mg+-SCNC2H5: one is with Mg+ being linked to the S atom and the other to the N atom. The former is more stable than the latter by only 0.23 eV. Both of the isomers have been shown to exist in the complex source employed in our experiments. On the other hand, only one stable structure is found for the complex Mg+-NCSC2H5 characterized by the Mg+-N linkage. In general, the photofragments are dominated by Mg+ at lambda > 400 nm, which decreases with decreasing wavelength accompanied by the increase in other photoproducts. In addition, the branching ratios of Mg+ to other photoproducts are nearly constant in the short wavelength region but decrease with decreasing wavelength. The observed photoreactions have been reasonably explained.     

Dioxygen activation by a low-valent cobalt complex employing a flexible tripodal N-heterocyclic carbene ligand

The novel versatile cobalt(I) tris-carbene complex [(TIMEN(xyl))Co]Cl (1) (where TIMEN = (tris[2-(3-arylimidazol-2-ylidene)ethyl]amine) reacts with CO, one-electron oxidizers such as CH(2)Cl(2), and O(2) to yield the cobalt complexes [(TIMEN(xyl))Co(CO)]Cl (2), [(TIMEN(xyl))Co(Cl)]Cl (3), and peroxo species [(TIMEN(xyl))Co(O(2))](BPh(4)) (5). All new complexes were fully characterized by (1)H NMR, UV/vis, and IR spectroscopy as well as superconducting quantum interference device (SQUID) magnetization measurements and single-crystal X-ray crystallography. The nucleophilic character of the eta(2)-bound dioxygen ligand in 5 was confirmed by density functional theory (DFT) studies and allows for oxygen-transfer reactions with electron-deficient organic substrates, such as benzoyl chloride.     

Quantum-mechanical effects and gate leakage current of nanoscale n-type FinFETs: A 2d simulation study

This paper simulates a kind of new sub-50 nm n-type double gate MOS nanotransistors by solving coupled Poisson-Schrödinger equations in a self-consistent manner with a finite element method, and presents a systematic simulation-based study on quantum-mechanical effects, gate leakage current of FinFETs. The simulation results indicate that the deviation from the classical model becomes more important as the gate oxide, gate length and Fin channel width becomes thinner and the Fin channel doping increases. Gate tunneling current density reduces with the body thickness decreasing. Excessive scaling increases the gate current below Fin thickness of 5 nm. The gate current can be dramatically reduced beyond 10¹⁷ cm⁻³ with the Fin body doping increasing. In order to understand the influence of electron confinement, quantum mechanical simulation results are also compared with the results from the classical approach. Our simulation results indicate that quantum mechanical simulation is essential for the realistic optimization of the FinFET structure.