Electronic structure calculations of small Al n (n=2–8) clusters

The electronic states of small Al _n (n=2–8) clusters have been calculated with a relativistic ab-initio MO-LCAO Dirac-Fock-Slater method using numerical atomic DFS wave-functions. The excitation energies were obtained from a ground state calculation of neutral clusters, and in addition from negative clusters charged by half an electron in order to account for part of the relaxation. These energies are compared with experimental photo-electron spectra.     

Relativistic effects on the electronic structure and volatility of group-8 tetroxides MO4, where M=Ru, Os, and element 108, Hs

The influence of relativistic effects on properties and volatility of the group-8 tetroxides MO4, where M=Ru, Os, and element 108, Hs, was studied on the basis of results of the fully relativistic (four component) and nonrelativistic density functional theory calculations. Relativistic effects were shown to increase bond strengths and decrease bond lengths in these molecules. They are responsible for a decrease in molecular polarizabilities and an increase in ionization potentials. The effects are much stronger in HsO4 than in the lighter congeners. Relativistic effects were also shown to slightly decrease dispersion interaction energies of RuO4, OsO4, and HsO4 with an inert (quartz or silicon nitride) surface, i.e., they increase volatility of these compounds as studied in the "one-atom-at-a-time" gas-phase chromatography experiments. They do, however, not influence the trend in group 8: both relativistically and nonrelativistically, volatility should change as RuO4相似文献   

Method for obtaining the rate coefficient of a second-order gas evolving reaction

The method is based on the measurement of pressures produced by collection of the gas during equal time intervals. It was applied to HCOOH decomposition in H₂SO₄.     

Investigation of radioactivity level in soil and drinking water samples collected from the city of Erzincan,Turkey

This study is part of an effort to assess the level of background radiation for Erzincan Province of eastern Turkey. Radionuclide activity concentrations in soil samples were measured through gamma-ray spectrometry and the average activities were determined as 8.93, 11.39, 281.94, and 9.52 Bq/kg for the radionuclides ²³⁸U, ²³²Th, ⁴⁰K, and ¹³⁷Cs, respectively. The average annual effective dose from these natural radioactivity sources (²³⁸U series, ²³²Th series and ⁴⁰K,) was calculated to be 27.9 μSv. Radioactivity levels in drinking and potable water samples were studied using a multi-channel low level proportional counter. The average gross alpha activity concentration was found to be 0.0477 Bq/L (min. 0.007 Bq/L; max. 0.421 Bq/L) and the average gross beta activity was measured as 0.104 Bq/L (min. 0.008 Bq/L; max. 1.806 Bq/L). These values lead to an average annual effective dose of 9.75 μSv from the alpha emitters and 56.34 μSv from the beta emitting radionuclides in water. The radioactivity levels in the water samples investigated were found to comply with the reference levels recommended by WHO and the regulations set forth by the Turkish Health Ministry.     

Functionalized orthoesters as powerful building blocks for the efficient preparation of heteroaromatic bicycles

By combining substituted anilines with functionalized orthoesters, an efficient and connective methodology for the preparation of benzoxazole, benzothiazole, and benzimidazole derivatives has been established. The versatility of this approach enables the development of new libraries of heterocycles containing multifunctional sites.     

Highly chemoselective reduction of carbonyl groups in the presence of aldehydes

The exquisite ability of diethylaluminum benzenethiolate to efficiently discriminate between aldehydes and other carbonyl functions enables the chemoselective in situ reduction of ketones and methyl esters in the presence of aldehydes. This potent strategy avoids the usual drawbacks of traditional protecting group methodologies and could be extended to various other transformations.     

M-shell satellite structure of W X-ray emission lines

The M-shell satellite structure of W X-ray emission lines excited by electron bombardment is investigated by a high resolution single crystal spectrometer, and the obtained structure is further compared with calculated transition energies obtained by the Relativistic Density Functional method. The transition hole states situated in the N- and O-shells—due to Coster–Kronig transitions—correspond to the parts of the spectra situated in the close neighbourhood of the diagram transition (0.7–4.4 eV).     

Recent progress in pillar[n]arene-based thin films on chemical sensor applications

Journal of Inclusion Phenomena and Macrocyclic Chemistry - Pillar[n]arene is one of the most favorited supramolecular materials that possess a special chiral structure. The major property of...     

Relativistic effects on atomic and molecular properties of the heaviest elements

Interaction of superheavy element 112 and its homolog Hg with inert and gold surfaces was studied on the basis of atomic and molecular fully-relativistic (4-component) DFT electronic structure calculations. Performance of additional non-relativistic calculations allowed one to demonstrate the role and magnitude of relativistic effects on adsorption energies and bond distances of the studied systems. For example, on quartz, element 112 will be stronger adsorbed than Hg by about 5 kJ/mol (or at 5 degrees higher temperatures) due to the stronger van der Waals interaction. This is caused by the relativistically contracted smallest atomic radius of element 112. Non-relativistically, the trend would be opposite. On surface of gold, element 112 will be about 20 kJ/mol weaker adsorbed than Hg (i.e., it will be deposited at about 100 degrees lower temperatures than Hg). Such a decrease in ΔH_ads comes at the account of the weaker interaction of the relativistically stabilized 7s_1/2(112) orbital with valence orbitals of gold. Still, the relatively large adsorption energy of element 112 is indicative that it is a transition metal forming intermetallic compounds with Au and other metals due to the involvement of the relativistically destabilized 6d orbitals. The influence of relativistic effects on the adsorption energy depends, however, on the adsorption position.