The mechanism of photocatalytic hydrogen production from gaseous methanol and water: IR spectroscopic approach

IR spectroscopic and volumetric study under reaction conditions of the mechanism of photocatalytic hydrogen production from gaseous methanol and water revealed that CO₂ and H₂ were produced by reaction between adsorbed CH₃O(ad) and H₂O. Another reaction path for H₂ production, CH₃ OH(ad) → H₂ + HCHO, was suggested which is dominant in the absence of water.     

On translation planes of orderq 3 that admit a collineation group of orderq 3

Let II be a translation plane of orderq ³, with kernel GF(q) forq a prime power, that admits a collineation groupG of orderq ³ in the linear translation complement. Moreover, assume thatG fixes a point at infinity, acts transitively on the remaining points at infinity andG/E is an abelian group of orderq ², whereE is the elation group ofG.In this article, we determined all such translation planes. They are (i) elusive planes of type I or II or (ii) desirable planes.Furthermore, we completely determined the translation planes of orderp ³, forp a prime, admitting a collineation groupG of orderp ³ in the translation complement such thatG fixes a point at infinity and acts transitively on the remaining points at infinity. They are (i) semifield planes of orderp ³ or (ii) the Sherk plane of order 27.     

On translation planes of orderq 3 that admit a collineation group of orderq 3, II

Let II be a translation plane of orderq ³ with kernel GF(q) that admits a collineation groupG of orderq ³ in the linear translation complement such thatG fixes a point at infinity and acts transitively on the remaining points at infinity.In this paper, we show that any such translation plane II is one of the following types of planes:     

Stability of crown ether complexes: a mo theoretical study

Calculation using CNDO/2 method have been performed for the crown ethers and their cation complexes. The photoelectron spectra of 18-crown-6 and 12-crown-4 are well described by the present MO calculations. The orbital interactions between the crown ligand and the cation indicate the importance of the charge transfer interaction for the complex formation. The destabilization energy due to the ring-shrinking (~ 0.5 eV) is very small compared with the complexation energy (5–8 eV). The stability of the complex was reasonably explained by the considering the hydrated species of the cation and the complex, indicating the important role of the solvation effect in the selectivity of the crown ether to the cation.     

Stable conformations of 12-crown-O3N and its Li+ complex in aqueous solution

Stable conformations of 12-crown-O3N and its Li complexes in aqueous solution were investigated. To calculate the free energy differences of conformers of 12-crown-O3N and its Li+ complex, our procedure was to make use of two programs, CONFLEX and BOSS. The former generates conformers, and the latter calculates the differences in free energy of solvation between two conformers in aqueous solution. It was confirmed that the present procedure is applicable in solving the question of what is the most stable conformation of 12-crown-O3N in aqueous solution. Results of the calculations suggest that the order of stability for conformers in a vacuum is different from that in aqueous solution. It was also confirmed that the coordination geometry of solvent waters to Li+ changes depending on the distance between the cation and the crown ring.     

Ab initio molecular orbital study on three feasible mechanisms for substitution of the vinylic carbon in F2C=C(OMs)BMe3−

A substitution on 2,2-difluorovinylic carbon was investigated by using ab initio molecular orbital calculations. Three feasible mechanisms, which are the S_N1-like, the S_N2-type and the addition-elimination mechanisms, were ex- amined for a model borate, 2,2-difluoro-1-mesyloxyvinyl(trimethyl)borate. Four TSs were obtained depending on the position of Li⁺ around the vinylborate although activation energies in the gas phase are rather high (ca. 30–40 kcal mol⁻¹) in comparison with that expected from the experimental conditions. It was confirmed at the SCRF-IPCM calculations that the solvent effect reduces the acti- vation energy of one S_N2-type mechanism very much (4. l kcal mol⁻¹ at the B3LYP/6-31+G^*//RHF/6-31+G^/s* level of theory) while those for the other mechanisms do not change very much. Therefore, the S_N2-type mechanism is applicable to the substitution reaction observed for the vinylborate.     

On the Sherk plane

In this paper, we characterize the Sherk plane as the only non-semifield translation plane of order 27 that admits an abelian group of order 27 in the translation complement.     

Development of ion transportation, extraction and neutralization systems for atomic beam resonance method

A device that produces a low-energy and largely spin polarized RI beam based on the atomic beam resonance method (RIABR) has been developed. We have performed measurements of stopping and drifting an incoming RI ion beam in a gas chamber, extraction of the ions into a vacuum region, and neutralization of the extracted low-energy ion beam. The drift efficiency of RI ions in a gas and the extraction efficiency at a Laval-type glass nozzle were found to be 0.72±0.04 and 0.033, respectively. The result of the experiment for the neutralization is also discussed.     

Surface electronic structure of binary metal oxide catalyst ZrO2/SiO2

The surface electronic structure of the binary metal oxide ZrO₂/SiO₂ was studied by means of XPS and the decrete variational (DV) Xα cluster model calculation. The results show that when ZrO₂, was supported on SiO₂, the SiO bond of SiO₂, neighboring ZrO₄, became stronger and that the Brönsted acid site H which is located on the SiO₄ unit exhibits stronger acidity.