Random field effects in the three dimensional Ising magnet: Fe x Zn1−x F2

We have carried out a comprehensive neutron scattering study of random field effects in the diluted three dimensional Ising antiferromagnet Fe _x Zn_1–x F₂ withx=0.35 and 0.5. Emphasis is on the global trands from the small to the large random field regimes. It is found, as in previous experiments, that when the system is cooled in a field it evolves from the high temperature paramagnetic state to a low temperature domain wall state. The low temperature peaks are well-described by Lorentzian squared profiles although for thex=0.5 sample extinction made the measurements difficult. In both samples, the results show that in the field-cooled state the correlation length varies asH ^–v withv=2.2±0.1. In thex=0.35 sample this power law holds over a length scale varying from 2 to 1500 lattice constants. At low fields pretransitional behavior similar to that observed previously in Fe_0.6Zn_0.4F₂ is found. AtT _N (H=0) it is found that the correlation length also scales algebraically withH but withv=0.86±0.04. Pronounced history-dependent effects are observed below the phase boundary determined by the peak in the critical scattering. For example, on cooling in zero-field, raising the field and then warming, long range order survives up to the phase boundary; at this point it appears to convert abruptly into the finite correlation length field cooled state although elucidation of the explicit nature of this transition is complicated by rounding due to a concentration gradient. These results are discussed in the context of recent theories incorporating metastability effects as well as recent experiments.     

Water-assisted oxo mechanism for heme metabolism

A mechanism of heme metabolism by heme oxygenase (HO) is discussed from B3LYP density functional theory calculations. The concerted OH group attack to the alpha-carbon by the iron-hydroperoxo species is investigated using a model with full protoporphyrin IX to confirm our previous conclusion that this species does not have sufficient oxidizing power for heme oxidation (J. Am. Chem. Soc. 2004, 126, 3672). Calculated activation energies and structures of the intermediates and transition state for this process remain unchanged from those for a small model with porphine in the previous study, which shows that the inclusion of the side chain of the porphyrin ring is not essential in describing the OH group transfer. The activation barrier for a direct oxo attack to the alpha-carbon by an iron-oxo model is calculated to be 49.8 kcal/mol, the barrier height of which looks very high for the enzymatic reaction under physiological conditions. This large activation energy is due to a highly bent porphyrin structure in the transition state. However, a bridging water molecule plays an important role in reducing the porphyrin distortion in the transition state, resulting in a remarkable decrease of the activation barrier to 13.9 kcal/mol. A whole-enzyme model with about 4000 atoms is constructed to elucidate functions of the protein environment in this enzymatic reaction using QM/MM calculations. The key water molecule is fixed in the protein environment to ensure the low-barrier and regioselective heme oxidation. A water-assisted oxo mechanism of heme oxidation by heme oxygenase is proposed from these calculational results.     

Interpolation of contour intervals in Moire topography by phase modulation

A trial has been performed with respect to the interpolation of contour intervals in Moiré topography by making use of phase modulation. A simple mechanical system can bring improved results for the precise measurements of shape of a specimen.     

Attractivity in non-autonomous systems

We discuss some sufficient conditions for attractivity of a closed set by using Liapunov functions and show how to apply our results to the study of asymptotic behaviors of solutions in nonautonomous systems. We also discuss the convergence of solutions by the same idea. These results are extendable to functional differential equations.     

Control of molecular interactions by the hollow of coordination cages

Coordination self-assembly entities have been demonstrated to be useful and powerful alternatives for the construction of predefined and well-organized architectures. Self-assembled coordination cages, which possess an inner hydrophobic cavity, can be utilized to move substrates closer by encapsulation so enabling their interaction with each other and exhibiting of non-classical physical properties.     

Electroabsorption spectroscopy of 6-hydroxyquinoline doped in polymer films: Stark shifts and orientational effects

Stark absorption spectroscopy was applied to 6-hydroxyquinoline (6-HQ) doped in polymer films of poly(methyl methacrylate) (PMMA) and poly(vinyl alcohol) (PVA) at temperatures of 50-300 K. The electroabsorption (E-A) spectrum of 6-HQ markedly depends on temperature in a PMMA film. The polarization dependence as well as the temperature dependence of the E-A spectra reveals that 6-HQ is oriented along the direction of the applied electric field at room temperature in a PMMA film. As the temperature becomes lower, the field-induced orientation of 6-HQ is restricted, and only the Stark shift induced by a change in electric dipole moment and in molecular polarizability is observed. On the other hand, E-A spectra of 6-HQ doped in a PVA film are essentially independent of temperature, suggesting that 6-HQ is not oriented along the electric field even at room temperature in PVA. These results show that the molecular motion of 6-HQ in a polymer film is very sensitive to the microenvironment of the surrounding matrix.     

External electric field effects on fluorescence of pyrene butyric acid in a polymer film: concentration dependence and temperature dependence

Fluorescence spectra and electrofluorescence spectra (plots of the electric field-induced change in fluorescence intensity as a function of wavelength) have been measured at different temperatures for pyrene butyric acid (PBA) in a PMMA film at different concentrations. At a low concentration of 0.5 mol % where fluorescence emitted from the locally excited state of PBA (LE fluorescence) is dominant, LE fluorescence spectra show only the Stark shift in the presence of an electric field (F), which results from the difference in molecular polarizability between the ground and emitting states. At a high concentration of 10 mol % where the so-called sandwich-type excimer fluorescence (EX(1)) is dominant, both EX(1) and LE fluorescence are quenched by F. Another fluorescence assigned to a partially overlapped excimer (EX(2)) also exists at room temperature, and this emission is enhanced by F. As the temperature decreases, three fluorescence emissions whose electric field effects are different from each other become clear besides EX(1) and LE fluorescence, indicating that at least five fluorescence components exist at high concentrations at low temperatures. At a medium concentration of 5 mol % where EX(1) is comparable in intensity to the LE fluorescence, the intensity of EX(1) is not affected by F at any temperature, but LE fluorescence and EX(2) are markedly influenced by F at room temperature, and four fluorescence emissions are confirmed at low temperatures.     

Microscopic Studies of 2H-NbSe2 Probed by Positive Muon

Abstract

The microscopic state of the positively charged light particle in the transition metal dichalcogenide 2H-NbSe₂ was studied using the muon spin relaxation method (μ⁺SR) and muon level crossing resonance method (μ-LCR). Muons are expected to stay at interlayer position and behaves as a hydrogen like intercalant. We discuss the relation between conduction electron properties and the muon's behavior.