Ab Initio Study of Electroweak Responses of 4He

In this contribution, we discuss the electroweak responses of ⁴He based on a full four-body calculation. The wave function of the ground state is obtained accurately using an explicitly correlated basis. Four-body final states are expressed in a superposition of many basis functions including configurations which have 3+1 and 2+1+1 cluster partitions of four-nucleon system explicitly. The continuum is properly treated by taking the two approaches: one is the complex scaling method and the other is the microscopic R-matrix method. The calculated photoabsorption cross sections agree up to the rest energy of a pion. The spin–dipole strength function is also presented and its relationship between the spectrum of ⁴He is discussed.     

Background story of the invention of efficient blue InGaN light emitting diodes (Nobel Lecture)

Shuji Nakamura discovered p‐type doping in Gallium Nitride (GaN) and developed blue, green, and white InGaN based light emitting diodes (LEDs) and blue laser diodes (LDs). His inventions made possible energy efficient, solid‐state lighting systems and enabled the next generation of optical storage. Together with Isamu Akasaki and Hiroshi Amano, he is one of the three recipients of the 2014 Nobel Prize in Physics. In his Nobel lecture, Shuji Nakamura gives an overview of this research and the story of his inventions *** .

     

Deterministic random walks on finite graphs

The rotor‐router model, also known as the Propp machine, is a deterministic process analogous to a random walk on a graph. Instead of distributing tokens to randomly chosen neighbors, the Propp machine deterministically serves the neighbors in a fixed order by associating to each vertex a “rotor‐router” pointing to one of its neighbors. This paper investigates the discrepancy at a single vertex between the number of tokens in the rotor‐router model and the expected number of tokens in a random walk, for finite graphs in general. We show that the discrepancy is bounded by O (mn) at any time for any initial configuration if the corresponding random walk is lazy and reversible, where n and m denote the numbers of nodes and edges, respectively. For a lower bound, we show examples of graphs and initial configurations for which the discrepancy at a single vertex is Ω(m) at any time (> 0). For some special graphs, namely hypercube skeletons and Johnson graphs, we give a polylogarithmic upper bound, in terms of the number of nodes, for the discrepancy. © 2014 Wiley Periodicals, Inc. Random Struct. Alg., 46,739–761, 2015     

A novel ruthenium sensitizer with a hydrophobic 2-thiophen-2-yl-vinyl-conjugated bipyridyl ligand for effective dye sensitized TiO2 solar cells

A hydrophobic and 2-thiophen-2-yl-vinyl-conjugated ruthenium complex, cis-Ru(dhtbpy)(dcbpy)(NCS)2 [dhtbpy = 4,4'-di(hexylthienylvinyl)-2,2'-bipyridyl; dcbpy = 4,4'-dicarboxy-2,2'-bipyridyl], was newly designed, synthesized and applied successfully to sensitization of nanocrystalline TiO2-based solar cells, giving a conversion efficiency of 9.5% under irradiation with AM 1.5 solar light.     

Enhanced delivery of retinoic acid to skin by cationic liposomes

We studied the delivery of retinoic acid to skin by using cationic liposomes consisting of double-chained cationic surfactant, phosphatidylcholine (PC) and retinoic acid in excised guinea pig dorsal skin. Egg yolk PC liposomes contaning retinoic acid at a molar ratio of 4 : 1 increased the delivery of retinoic acid about two-fold, compared with its addition as an isopropyl myristate solution. Cationic liposomes containing 1,2-dioleoyl-3-trimethylammonium propane (DOTAP) further enhanced the incorporation dependent on the DOTAP content. Liposomes consisting of DOTAP, egg yolk PC, and retinoic acid at a molar ratio of 2 : 2 : 1 induced a 3.7-fold increase in the skin incorporation compared with the egg yolk PC liposomes without DOTAP. Significant difference was not observed when either dimyristoylphosphatidylcholine (DMPC) or dipalmitoylphosphatidylcholine (DPPC) was used instead of egg yolk PC as well as when dimethyldipalmitylammonium was used instead of DOTAP. These results suggest the potential of the use of the cationic liposomes for the intradermal delivery of lipophilic drugs like retinoic acid.     

Deuterium kinetic isotope effects in gas-phase S(N)2 and E2 reactions: comparison of experiment and theory

The competition between bimolecular nucleophilc substitution and base-induced elimination is investigated through kinetic isotope effect measurements for gas-phase reactions of RCl + ClO- (R = methyl, ethyl, isopropyl, and tert-butyl) utilizing a FA-SIFT instrument. The overall reaction rate constants and the kinetic isotope effect for the reaction of C2H5Cl + ClO- are compared to computational results. [Hu, W. P.; Truhlar, D. G. J. Am. Chem. Soc. 1996, 118, 860.] Experimental results show that as the degree of substitution in the neutral reactant increases the E2 channel becomes dominant. The systematic change in the overall kinetic isotope effects indicates that, for the reaction of ClO- with C2H5Cl, both the SN2 and E2 pathways do occur, as predicted by computation; however the experimental reaction rate constants and KIE deviate strongly from the computational result.     

Mechanisms of oscillations and formation of nano-scale layered structures in induced co-deposition of some iron-group alloys (Ni-P, Ni-W, and Co-W), studied by an in situ electrochemical quartz crystal microbalance technique

We have investigated mechanisms of oscillations and formation of nano-scale layered structures in induced co-deposition of some iron-group alloys (Ni-P, Ni-W, and Co-W) that have unique properties and are widely used in industries. Detailed in situ electrochemical quartz crystal microbalance (EQCM) experiments have revealed that the electrodeposition (induced co-deposition) of the alloys has negative differential resistances (NDRs), from which the oscillations and the layer-structure formation arise. The NDRs, however, cannot necessarily be seen in current-potential curves owing to overlap of hydrogen evolution current, indicating that the oscillations are of a hidden-NDR (H-NDR) type. The EQCM experiments have also shown that electrolyte components (such as H2PO2- and WO4(2-)) or related species are adsorbed at the electrode (deposit) surface and act as a promoter for the co-deposition reaction and that the NDRs arise from desorption of the adsorbed promoter. Interestingly, the adsorbed promoter is drawn into the deposition reaction itself, thus resulting in the alloy deposits. This mechanism was supported by in situ EQCM investigations of the oscillation as well as Auger electron spectroscopic (AES) analyses of deposits formed during the oscillation. The present work has for the first time clarified a general mechanism for the induced co-deposition reactions of some industrially important iron-group alloys (Ni-P, Ni-W, and Co-W).     

Enantioselective photooxidation of a sulfide by a chiral ruthenium(II) complex immobilized on a montmorillonite clay surface: the role of weak interactions in asymmetric induction

The present work pursued a possibility that enantioselectivity was achieved through weak intermolecular interactions between a catalyst and a substrate. For that purpose, we studied the photooxidation of alpha-ethylbenzyl phenyl sulfide catalyzed by a polypyridyl ruthenium(II) complex as a chiral photosensitizer. No covalent bonding was formed between a catalyst and a substrate, because the complexes used ([Ru(phen)(3)](2+) or [Ru(bpy(3))(2+)]) were coordinatively saturated. Enantiomer excess (ee) was attained to be 30% when a chiral photosensitizer was immobilized on montmorillonite clay. It was even improved to 43% in the presence of an additional chiral auxiliary, dibenzoyl-D(+)-tartaric acid. Notably, no enantioselectivity was achieved when the reaction took place in homogeneous solutions. The ab initio calculations were performed on the stability of an associate composed of a catalyst (metal complex) and a product (sulfoxide) to obtain a clue to reaction mechanisms. The calculations suggest that chiral discrimination is achieved even through noncovalent interactions between a substrate and a chiral sensitizer when the attacking direction by a substrate toward a catalyst is limited sterically on a solid surface.