Destruction of a solid film under the action of ultrashort laser pulse

Molecular-dynamics (MD) simulation of the destruction of a crystal film heated by a femtosecond laser pulse was carried out. Heating is assumed to be instantaneous, because there is no time for the material to be displaced during the pulse. Film destruction is caused by the interaction of unloading waves. It can be considered as a model of a more complex process of splitting out of a thin surface layer from a massive target in the case where the layer remains solid after heating. It was found that the crystal order is broken due to the stretching strains and to the strong anisotropy of residual stress, resulting in a bipartition of the layer separating from the target. The lattice stretching and the formation of anisotropic stresses are due to the expansion of a heated lattice.     

Synthesis, characterization, and photochemical properties of azobenzene-conjugated Ru(II) and Rh(III) bis(terpyridine) complexes

We synthesized azobenzene-conjugated bis(terpyridine) Ru(II) and Rh(III) mononuclear and dinuclear complexes and investigated their photochemical properties on excitation of the azo pi-pi band upon 366 nm light irradiation. The Ru mononuclear complex underwent trans-to-cis photoisomerization to reach the photostationary state with only 20% of the cis form, while the Ru dinuclear complex did not isomerize at all photochemically. On the other hand, the mononuclear and dinuclear Rh complexes showed almost complete trans-to-cis photoisomerization behavior. Cis forms of the Rh complexes thermally returned to the trans form at a much slower rate than those of organic azobenzenes, but they did not isomerize photochemically. The reduction potential of the cis forms was 80 mV more negative than that of the trans forms. The photoisomerization quantum yields of the Rh complexes were strongly dependent on the polarity, viscosity, and donor site of the solvents as well as the size of the counterions. We investigated the photoisomerization process of these complexes using femtosecond absorption spectroscopy. For the Rh complexes, we observed S(n) <-- S(2) and S(n) <-- S(1) absorption bands similar to those of organic azobenzenes. For the Ru complexes, we observed very fast bleaching of the MLCT band of the Ru complex, which indicated that the energy transfer pathway to the MLCT was the primary cause of the depressed photoisomerization. The electronic structures, which were estimated from ZINDO molecular orbital calculation, supported the different photochemical reaction behavior between the Ru and Rh complexes.     

Chemoselective Oxidation of Secondary Hydroxy Functions Catalyzed by [PMo12O40]3-[C5H5N+(CH2)15 CH3]3

Abstract

The epoxidation of allylic alcohols with H₂O₂ catalyzed by a new Mo-species, [PMo₁₂O₄₀]^3?[C₅H₅N⁺(CH₂)₁₅CH₃]₃ (MPCP), prepared from 12-molybdatophosphoric acid (H₃PMo₁₂O₄₀) and cetylpyridinium chloride [C₅H₅N⁺(CH₂)₁₅CH₃ · Cl^?], has recently rep0rted.) The high regioselectivity for the epoxidation by this MPCP-H₂O₂ system was comparable to that of Sharpless method using t-BuOOH as oxidant.