Magnetic resonance experiments in NiBr2 at high frequencies and high magnetic fields

By performing magnetic resonance experiments in NiBr₂ at high frequencies and magnetic fields, we have observed a resonance line which we relate to a helimagnetic phase, and an antiferromagnetic resonance line corresponding to an antiferromagnetic phase with strong out-of-plane anisotropy and small in-plane anisotropy.     

The quark mixing matrix in a composite model

The generalized mixing matrix of quarks is computed based on a composite model of quarks and leptons. Among potentials between constituent particles examined V(r) = Ar^s (As > 0) and A ln r (A > 0), it is shown that potentials with exponent 0 ? s ? 3 or ln r are consistent with current experimental data for the mixing matrix elements.     

Polymerization of substituted acetylenes by various rhodium catalysts: Comparison of catalyst activity and effect of additives

This research deals with comparison of the activity of various Rh catalysts in the polymerization of monosubstituted acetylenes and the effect of various amines used in conjunction with [Rh(nbd)Cl]₂ in the polymerization of phenylacetylene. A zwitterionic Rh complex, Rh⁺(nbd)[(η⁶‐C₆H₅)B^?(C₆H₅)₃] ( 3 ), was able to polymerize phenylacetylene ( 5a ), t‐butylacetylene ( 5b ), N‐propargylhexanamide ( 5c ) and n‐hexyl propiolate ( 5d ), and displayed higher activity than the other catalysts examined, that is [Rh(nbd)Cl]₂ ( 1 ), [Rh(cod)(O‐o‐cresol)]₂ ( 2 ), and Rh‐vinyl complex ( 4 ). Monomers 5a and 5c polymerized virtually quantitatively or in fair yields with all these catalysts, while monomer 5b was polymerizable only with catalyts 3 and 4 . Monomer 5d did not polymerize in high yields with these Rh complexes. The catalytic activity tended to decrease in the order of 3 > 4 > 2 > 1 . Although polymerization of 5a did not proceed at all in toluene with [Rh(nbd)Cl]₂ alone, it smoothly polymerized in the presence of various amines as cocatalysts. The polymerization rate as well as the molecular weight of polymer depended on the basicity and steric bulkiness of amines. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4530–4536, 2005     

Microscopic evidence for a new type of ordering of spin components in a random mixture with competing magnetic anisotropies

The Mössbauer spectroscopy was applied on a random mixture of two kinds of magnetic ions with competing anisotropies, Fe_1?xCo_xCl₂·2H₂O. The Mössbauer spectra observed in the Co(Fe)-rich antiferromagnetic (AF) phase near the tetracritical point show that, although the m₂(m₁) spin component parallel to the easy axis of pure FeCl₂·2H₂O(CoCl₂·2H₂O) has no long-range order in this phase (from the neutron diffraction experiment), the m₂(m₁) spin component contributes to the magnetic hyperfine field at ⁵⁷Fe nuclei as well as the m₁(m₂) spin component (which has a long-range order). This fact indicates that the m₂(m₁) spin components exists in the Co(Fe)-rich AF phase near the tetra-critical point at least in a time scale of ～ 10^?8s. This result predicts that the antiferromagnetic ordering in the Co(Fe)-rich AF phase is a new type one. The new phase observed in the intermediate concentration region is demonstrated as the “mixed ordering” phase.     

UV photoelectron spectra and sum rule consideration: Out-of-plane orbitals of unsaturated compounds with planar-skeleton structure

He(l) photoelectron spectra are presented for various planar unsaturated aliphatic compounds such as mono- and di-methyl substituted ethylenes, alkyl aldehydes, chloro-substituted aldehydes, ketones and alkyl acids. Each photoelectron spectrum is resolved into individual bands by considering the band shape, the relative intensity and the number of p-type localized MO's (LO's). The sum rule previously proposed on vertical ionization energies by the present authors is applied to the photoelectron bands associated with out-of-plane LO's. In each compound, a partial sum P(a″) is obtained over all the out-of-plane LO's and it is shown that the calculated P(a″) value is in good agreement with the experimental one which may be obtained by an appropriate sum of vertical ionization energies with negative signs.     

Quasielastic neutron scattering in the high-field phase of a Haldane antiferromagnet

Inelastic neutron scattering experiments on the Haldane-gap quantum antiferromagnet Ni(C5D14N2)2-N3(PF6) are performed in magnetic fields below and above the critical field H(c) at which the gap closes. Quasielastic neutron scattering is found for H>H(c), indicating topological excitations in the high-field phase.     

Field-induced three- and two-dimensional freezing in a quantum spin liquid

Field-induced commensurate transverse magnetic ordering is observed in the Haldane-gap compound Ni(C(5)D(14)N(2))2N(3)(PF(6)) by means of neutron diffraction. Depending on the direction of applied field, the high-field phase is shown to be either a three-dimensional ordered Néel state or a short-range ordered state with dominant two-dimensional spin correlations. The structure of the high-field phase is determined, and properties of the observed quantum phase transition are discussed.     

Study on selective adsorption of deuterium on boron nitride using photon-stimulated ion-desorption

Adsorption behavior of atomic deuterium on a hexagonal boron nitride (h-BN) thin film is studied by photon-stimulated ion desorption (PSID) of D⁺ and near edge X-ray absorption fine structure (NEXAFS) at the B and N K-edges. After the adsorption of atomic deuterium, D⁺ desorption yield η(hν) shows clear enhancement at the B K-edge and almost no enhancement at the N K-edge. NEXAFS spectra show a large change in the B K-edge and a small change in the N K-edge after the adsorption. We propose selective adsorption of atomic deuterium on the h-BN thin film based on the experimental results, and mention the effectiveness of applying the PSID method with X-ray to study hydrogen storage materials.     

Synthesis and adsorptivity of acryloylmorpholine resin to various fission product elements in nitric acid media

A novel silica-supported resin with a cyclic monoamide of polymerized 4-acryloylmorpholine(Silica-AM) was synthesized, and adsorptivity to metal ions of major fission products(FP) was examined in HNO3 and HCl solutions. Silica-AM has a carbonyl oxygen atom outside of the 6-membered morpholine ring, and a cyclic structure that is different than other cyclic monoamide resins we have studied. These include polyvinylpolypyrrolidone(PVPP) and poly-N-vinyl-ε-caprolactam(VEC), both of which have coordinative carbonyl groups included in the ring. Silica-AM was similar to a cyclic monoamide we have reported because it exhibited adsorption to Pd(Ⅱ) and Re(VⅡ) in HNO3 of a particularly low concentration range. Silica-AM has an ether oxygen atom included in the ring as well. Considering the difference in the chemical structures of Silica-AM and other cyclic monoamide resins, it was suggested that oxygen atoms in the carbonyl group and in ether may be main contributors to Silica-AM's respective adsorptions to Pd(Ⅱ) and Re(VⅡ), and Mo(VI) and Zr(IV). Our results imply that the contribution of the two types of oxygen atoms to adsorption is more observable in an HCl system. The contribution of the ether oxygen atom to the adsorption of Pd(Ⅱ) was also suggested from our study on crystal prepared from 4-acetylmorpholine and palladium nitrate.     

Molecular design of polymer coatings capable of photo-triggered stress relaxation via dynamic covalent bond exchange

Polymer coatings are frequently used to modify surface properties of inorganic substrates. However, the disparity in physical properties between polymer film and substrate often leads to residual stress development, which can be deleterious to the overall performance of coated materials. This work reports the molecular design of polymer films that dissipate stress upon irradiation with ultraviolet (UV) light. These polymers are synthesized by post-polymerization modification of the reactive polymer, poly(2-vinyl-4,4-dimethyl azlactone), to introduce dynamic crosslinks capable of light-initiated addition transfer fragmentation chemistry. Using a custom-built optical cantilever, contrasting film stress responses are observed between films containing dynamic bonds and analogous control films after UV light irradiation, which indicate successful stress relaxation. Further experiments demonstrate the complete relaxation of residual stress in dynamic films after an extended exposure, thereby generating a “stress-free” film. Films fabricated using this approach can be easily tailored to incorporate additional moieties to introduce desired surface properties for future application in a wide array of coatings.