Effect of a thin dielectric layer on terahertz transmission characteristics for metal hole arrays

We studied the role of surface-plasmon polaritons (SPPs) in a bandpass transmission property of two-dimensional metal hole arrays (2D-MHAs) by investigating the effect of thin dielectric layers on the 2D-MHA surfaces. We measured zero-order transmission spectra of the 2D-MHAs by changing the thickness of the dielectric layer and found that the bandpass transmission peak shifted to the lower-frequency side with increasing layer thickness, owing to the change of the resonant frequency of the SPP. This result shows that SPPs play a crucial role in the transmission property of 2D-MHAs in the terahertz region.     

Electronic origin of the surface reconstruction of the (001) surface of Cr,Mo and W

The d-band effects on the reconstruction of the (001) surface of Cr, Mo and W are discussed with a tight-binding model. Response functions corresponding to some models for the reconstruction and their q-dependence are calculated by using Haydrock et al.'s recursion method. The present calculation shows that an energy gain by broadening the surface state peak near the Fermi energy is most remarkable for the model proposed by Debe and King, and therefore gives a theoretical support to it. The energy gain is attributed to an enhancement in the bonding property by pairing of surface atoms in the Debe and King model. Response functions without an electron-phonon matrix element (EPME) are also calculated, which show only a very weak q-dependence. Detailed discussions are given on the mode dependence, that is, on the effect of EPME.     

On the property of eigenvalues of some infinitesimal generator

We analyze a class of finite dimensional birth-and-death processes. New conclusions are reached for the property of the eigenvalues of the infinitesimal generator for these processes.     

Hydration properties of magnesium and calcium ions from constrained first principles molecular dynamics

We studied the solvation structures of the divalent metal cations Mg(2+) and Ca(2+) in ambient water by applying a Car-Parrinello-based constrained molecular dynamics method. By employing the metal-water oxygen coordination number as a reaction coordinate, we could identify distinct aqua complexes characterized by structural variations of the first coordination shell. In particular, our estimated free-energy profile clearly shows that the global minimum for Mg(2+) is represented by a rather stable sixfold coordination in the octahedral arrangement, in agreement with experiments. Conversely, for Ca(2+) the free-energy curve shows several shallow local minima, suggesting that the hydration structure of Ca(2+) is highly variable. Implications for water exchange reactions are also discussed.     

Hydration of alkali ions from first principles molecular dynamics revisited

Structural and dynamical properties of the hydration of Li(+), Na(+), and K(+) in liquid water at ambient conditions were studied by first principles molecular dynamics. Our simulations successfully captured the different hydration behavior shown by the three alkali ions as observed in experiments. The present analyses of the dependence of the self-diffusion coefficient and rotational correlation time of water on the ion concentration suggest that Li(+) (K(+)) is certainly categorized as a structure maker (breaker), whereas Na(+) acts as a weak structure breaker. An analysis of the relevant electronic structures, based on maximally localized Wannier functions, revealed that the dipole moment of H(2)O molecules in the first solvation shell of Na(+) and K(+) decreases by about 0.1 D compared to that in the bulk, due to a contraction of the oxygen lone pair orbital pointing toward the metal ion.     

Focusing effect measurements of artificial dielectric multilayer lens with metal rectangular chips for terahertz wave band

This paper presents the design and fabrication of an artificial multilayer lens comprising ten layers of metal rectangular chips on a cyclo olefin polymer, which has low loss in the terahertz band. Measurements of the focusing effect are also presented. The focusing effect is produced by the rectangular metallic chips which act as an electrical dipole. Simulations are performed using ANSYS HFSS. The lenses are fabricated by laser processing or semiconductor etching. The focusing effect is confirmed by measurement using terahertz near-field microscopy, although some discrepancies are observed between the simulated and measured results.     

Total syntheses of (+)-polygalolide a and (+)-polygalolide b: elucidation of the absolute stereochemistry and biogenetic implications

The total syntheses of (+)-polygalolide?A and (+)-polygalolide?B have been completed by using a carbonyl ylide cycloaddition strategy. Three of the four stereocenters, including two consecutive tetrasubstituted carbon atoms at C2 and C8, were incorporated through internal asymmetric induction from the stereocenter at C7 by a [Rh(2) (OAc)(4)]-catalyzed carbonyl ylide formation/intramolecular 1,3-dipolar cycloaddition sequence. The arylmethylidene moiety of these natural products was successfully installed by a Mukaiyama aldol-type reaction of a silyl enol ether with a dimethyl acetal, followed by elimination under basic conditions. We have also developed an alternative approach to the carbonyl ylide precursor based on a hetero-Michael reaction. This approach requires 18 steps, and the natural products were obtained in 9.8 and 9.3?% overall yields. Comparison of specific rotations of the synthetic materials and natural products suggests that polygalolides are biosynthesized in nearly racemic forms through a [5+2] cycloaddition between a fructose-derived oxypyrylium zwitterion with an isoprene derivative.     

Photocatalytic oxidation of propylene with molecular oxygen over highly dispersed titanium, vanadium, and chromium oxides on silica

Photocatalytic oxidation of propylene with molecular oxygen at room temperature was investigated over various silica-supported metal oxides with low loading. The photocatalytic active site is assumed to be the isolated tetrahedrally coordinated metal oxides in the ligand-to-metal charge-transferred state, such as (Mdelta- -OLdelta+). Photocatalytic epoxidation of propylene into propylene oxide was promoted over silica-supported V and Ti oxides at steady state. Over silica-supported Cr oxide, the propylene oxide formation rate was remarkably decreased with the time course in the reaction. The oxidation state and the coordination environment of the supported Ti, V, and Cr oxide species were determined by diffuse reflectance UV-vis spectroscopy (DRS) and electron spin resonance (ESR). During the photocatalytic oxidation, the oxidation state of the Ti4+ species was not varied. On the other hand, the V5+ species was partially reduced to V4+ and the Cr6+ species was successively reduced to Cr5+ and Cr3+. An isotopic tracer study of the C3H6-18O2 reaction suggests the difference of the active oxygen species between TiO2/SiO2 and V2O5/SiO2. The active oxygen species on TiO2/SiO2 is derived from molecular oxygen. On the other hand, the photogenerated products on V2O5/SiO2 incorporate the lattice oxygen of the surface metal oxide species. It is suggested that the kinds of terminal ligand (hydroxyl or oxo) of the tetrahedrally coordinated metal oxides on silica decide the active oxygen species in the photocatalytic oxidation. A photoinduced hole center on the monohydroxyl (SiO)3Ti-OH species activates molecular oxygen that reacts with propylene. In the case of the monooxo (SiO)3V=O and dioxo (SiO)2Cr=O2 species, the photoactivated lattice oxygen (OL-) directly reacts with propylene.     

ChemInform Abstract: Hydrogen Elimination and Solid‐State Reaction in Hydrogen‐Bonded Systems under Pressure: The Case of HBr.

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