I. Electron spin relaxation studies of manganese(II) complexes in acetonitrile. II. Nuclear spin relaxation studies of bromine in tetrabromomanganese(II) in acetonitrile

Magnetic resonance techniques have given us a powerful means for investigating dynamical processes in gases, liquids and solids. Dynamical effects manifest themselves in both resonance line shifts and linewidths, and, accordingly, require detailed analyses to extract desired information. The success of a magnetic resonance experiment depends critically on relaxation mechanisms to maintain thermal equilibrium between spin states. Consequently, there must be an interaction between the excited spin states and their immediate molecular environment which promote changes in spin orientation while excess magnetic energy is coupled into other degrees of freedom by non-radiative processes. This is well known as spin-lattice relaxation. Certain dynamical processes cause fluctuations in the spin state energy levels leading to spin-spin relaxation and, here again, the environment at the molecular level plays a significant role in the magnitude of interaction. Relatively few electron spin relaxation studies of solutions have been conducted and the present work is addressed toward the extension of our knowledge in this area and the retrieval of dynamical information from line shape analyses on a time scale comparable to diffusion controlled phenomena.

Specifically, the electron spin relaxation of three Mn⁺²3d⁵ complexes, Mn(CH₃CN)₆⁺², MnCl₄^-2 in acetonitrile has been studied in considerable detail. The effective spin Hamiltonian constants were carefully evaluated under a wide range of experimental conditions. Resonance widths of these Mn⁺² complexes were studied in the presence of various excess ligand ions and as a function of concentration, viscosity, temperature and frequency (X-band, ~9.5 Ԍ Hz and K-band, ~35 Ԍ Hz).

A number of interesting conclusions were drawn from these studies. For the Et₄NCl-₄^-2 system several relaxation mechanisms leading to resonance broadening were observed. One source appears to arise through spin-orbit interactions caused by modulation of the ligand field resulting from transient distortions of the complex imparted by solvent fluctuations in the immediate surroundings of the paramagnetic ion. An additional spin relaxation was assigned to the formation of ion pairs [Et₄N⁺…MnCl₄^-2] and it was possible to estimate the dissociation constant for this specie in acetonitrile.

The Bu₄NBr-MnBr₄^-2 study was considerably more interesting. As in the former case, solvent fluctuations and ion-pairing of the paramagnetic complex [Bu₄N⁺…MnBr₄^-2] provide significant relaxation for the electronic spin system. Most interesting, without doubt, is the onset of a new relaxation mechanism leading to resonance broadening which is best interpreted as chemical exchange. Thus, assuming that resonance widths were simply governed by electron spin state lifetimes, we were able to extract dynamical information from an interaction in which the initial and final states are the same

MnBr₄^-2 + Br^- = MnBr₄^-2 + Br^-.

The bimolecular rate constants were obtained at six different temperatures and their magnitudes suggested that the exchange is probably diffusion controlled with essentially a zero energy of activation. The most important source of spin relaxation in this system stems directly from dipolar interactions between the manganese 3d⁵ electrons. Moreover, the dipolar broadening is strongly frequency dependent indicating a deviation between the transverse and longitudinal relaxation times. We are led to the conclusion that the 3d⁵ spin states of ion-paired MnBr₄^-2 are significantly correlated so that dynamical processes are also entering the picture. It was possible to estimate the correlation time, ^Td, characterizing this dynamical process.

In Part II we study nuclear magnetic relaxation of bromine ions in the MnBr4-2-Bu4NBr-acetonitrile system. Essentially we monitor the 79Br and 81Br linewidths in response to the [MnBr4-2]/[Br-] ratio with the express purpose of supporting our contention that exchange is occurring between "free" bromine ions in the solvent and bromine in the first coordination sphere of the paramagnetic anion. The complexity of the system elicited a two-part study: (1) the linewidth behavior of Bu4NBr in anhydrous CH3CN in the absence of MnBr4-2 and (2) in the presence of MnBr4-2. It was concluded in study (1) that dynamical association, Bu4NBr k1= Bu4N+ + Br-, was modulating field-gradient interactions at frequencies high enough to provide an estimation of the unimolecular rate constant, k1. A comparison of the two isotopic bromine linewidth-mole fraction results led to the conclusion that quadrupole interactions provided the dominant relaxation mechanism. In study (2) the "residual" bromine linewidths for both 79Br and 81Br are clearly controlled by quadrupole interactions which appear to be modulated by very rapid dynamical processes other than molecular reorientation. We conclude that the "residual" linewidth has its origin in chemical exchange and that bromine nuclei exchange rapidly between a "free" solvated ion and the paramagnetic complex, MnBr4-2.

Theoretical model for a periodically driven semiconductor laser subject to optical feedback from a microcantilever

We propose a theoretical model for analyzing the dynamics of a periodically driven semiconductor laser subject to optical feedback from a microcantilever. We numerically investigate the temporal evolution of the light intensity of the semiconductor laser, and we show the interspikes of the light intensity. These interspikes of light intensity are also demonstrated in our experiment. The validity of the theoretical model is verified. The observed phenomenon has a potential application for resonant sensing. (C) 2008 Optical Society of America.

Preparation, characterization and gas sensing properties of lead tetra-(tert-butyl)-5,10,1 5,20-tetraazaporphyrin spin-coating films

A spin-coated film of lead tetra-(tert-butyl)-5,10,15,20-tetraazaporphyrin complex (PbTAP(t-Bu)(4)) was obtained and characterized by IR spectra, absorption spectra and atomic force microscopy. The response and recovery characteristics of the film to NH3, NO2 and C2H5OH vapor were investigated at room temperature. In addition, the reversibility and stability of the film to NH3 were also studied. The results indicate that the PbTAP(t-Bu)(4) derivative can be exploited as an NH3 sensor at room temperature. (c) 2007 Elsevier B.V. All rights reserved.

Transparent Ni2+-doped MgO-Al2O3-SiO2 glass ceramics with broadband infrared luminescence

We report on transparent Ni2+-doped MgO-Al2O3-SiO2 glass ceramics with broadband infrared luminescence. Ni2+-doped MgO-Al2O3-SiO2 glass is Prepared by using the conventional method. After heat treatment at high temperature, MgAl2O4 crystallites are precipitated, and their average size is about 4.3nm. No luminescence is detected in the as-prepared glass sample, while broadband infrared luminescence centred at around 1315nm with full width at half maximum (FWHM) of about 300nm is observed from the glass ceramics. The observed infrared emission could be attributed to the T-3(2g)(F-3) -> (3)A(2g)(F-3) transition of octahedral Ni2+ ions in the MgAl2O4 crystallites of the transparent glass ceramics. The product of the fluorescence lifetime and the stimulated emission cross section is about 1.6 X 10(-24) s cm(2).

A new method of modeling cladding band structure of air-guiding photonic crystal fibers

Cladding band structure of air-guiding photonic crystal fibers with high air-filling fraction is calculated in terms of fiber shape variation. The fundamental photonic band gap dependence on structure parameters, air-filling fraction and spacing, is also investigated. The numerical results show that the band gap edges shift toward longer wavelength as the air-filling fraction is increased, whereas the relative band gap width increases linearly. For a fixed air-filling fraction, the band gap edges with respect to spacing keep constant. With this method, the simulation results agree well with the reported data. © 2007 Elsevier B.V. All rights reserved.

A novel polarization modulator for a Moire system with grating imaging

A polarization modulator based on splitting with a Savart plate and rotation of an analyzer for a moire system with grating imaging is presented, and its modulation principle is analyzed. The polarization modulator is simple and achromatic. It is composed of a polarizer, a Savart plate, and an analyzer. The polarizer and the Savart plate are placed in front of the index grating to split the image of the scale grating in the moire system. The analyzer is placed behind the grating and rotated to realize the modulation of the moire signal. The analyzer can be rotated either continually with high speed or step by step with low speed to form different modulation modes. The polarization modulator makes the moire system insensitive to the change of initial intensity. In experiments, we verified the usefulness of the polarization modulator.

Band structure of photonic crystal fibers with silica rings in triangular lattice

The characteristics of the cladding band structure of air-core photonic crystal fibers with silica rings in triangular lattice are investigated by using a standard plane wave method. The numerical results show that light can be localized in the air core by the photonic band gaps of the fiber. By increasing the air-filling fraction, the band gap edges of the low frequency photonic band gaps shift to shorter wavelength.. whereas the band gap width decreases linearly. In order to make a specified light fall in the low frequency band gaps of the fiber, the interplay of the silica ring spacing and the air-filling fraction is also analyzed. It shows that the silica ring spacing increases monotonously when the air-filling fraction is increased, and the spacing range increases exponentially. This type fiber might have potential in infrared light transmission. (c) 2006 Elsevier B.V. All rights reserved.

The Bay Scallop, Argopecten irradians, Massachusetts Through North Carolina: Its Biology and the History of Its Habitats and Fisheries

This article covers the biology and the history of the bay scallop habitats and fishery from Massachusetts to North Carolina. The scallop species that ranges from Massachusetts to New York is Argopecten irradians irradians. In New Jersey, this species grades into A. i. concentricus, which then ranges from Maryland though North Carolina. Bay scallops inhabit broad, shallow bays usually containing eelgrass meadows, an important component in their habitat. Eelgrass appears to be a factor in the production of scallop larvae and also the protection of juveniles, especially, from predation. Bay scallops spawn during the warm months and live for 18–30 months. Only two generations of scallops are present at any time. The abundances of each vary widely among bays and years. Scallops were harvested along with other mollusks on a small scale by Native Americans. During most of the 1800’s, people of European descent gathered them at wading depths or from beaches where storms had washed them ashore. Scallop shells were also and continue to be commonly used in ornaments. Some fishing for bay scallops began in the 1850’s and 1860’s, when the A-frame dredge became available and markets were being developed for the large, white, tasty scallop adductor muscles, and by the 1870’s commercial-scale fishing was underway. This has always been a cold-season fishery: scallops achieve full size by late fall, and the eyes or hearts (adductor muscles) remain preserved in the cold weather while enroute by trains and trucks to city markets. The first boats used were sailing catboats and sloops in New England and New York. To a lesser extent, scallops probably were also harvested by using push nets, picking them up with scoop nets, and anchor-roading. In the 1910’s and 1920’s, the sails on catboats were replaced with gasoline engines. By the mid 1940’s, outboard motors became more available and with them the numbers of fishermen increased. The increases consisted of parttimers who took leaves of 2–4 weeks from their regular jobs to earn extra money. In the years when scallops were abundant on local beds, the fishery employed as many as 10–50% of the towns’ workforces for a month or two. As scallops are a higher-priced commodity, the fishery could bring a substantial amount of money into the local economies. Massachusetts was the leading state in scallop landings. In the early 1980’s, its annual landings averaged about 190,000 bu/yr, while New York and North Carolina each landed about 45,000 bu/yr. Landings in the other states in earlier years were much smaller than in these three states. Bay scallop landings from Massachusetts to New York have fallen sharply since 1985, when a picoplankton, termed “brown tide,” bloomed densely and killed most scallops as well as extensive meadows of eelgrass. The landings have remained low, large meadows of eelgrass have declined in size, apparently the species of phytoplankton the scallops use as food has changed in composition and in seasonal abundance, and the abundances of predators have increased. The North Carolina landings have fallen since cownose rays, Rhinoptera bonsais, became abundant and consumed most scallops every year before the fishermen could harvest them. The only areas where the scallop fishery remains consistently viable, though smaller by 60–70%, are Martha’s Vineyard, Nantucket, Mass., and inside the coastal inlets in southwestern Long Island, N.Y.

Determinação por ultrassom de constantes elásticas de pastilhas de alumina utilizadas em varetas combustíveis de reatores nucleares.

Pastilhas de dióxido de urânio (UO2) são empregadas como combustível nos reatores nucleares de potência, onde as condições operacionais introduzem elevados gradientes térmicos nas pastilhas. Potências elevadas propiciam a fusão da parte central das pastilhas. O inchamento das pastilhas de dióxido de urânio (UO2), decorrente dos produtos de fissão, pode causar o trincamento do material, em função disso, o estudo do seu comportamento mecânico é importante. Esse trabalho avaliou a aplicação de método ultrassônico na obtenção de constantes elásticas. Em função das dificuldades no manuseio do material nuclear, optou-se por um estudo comparativo em pastilhas de alumina (Al2O3). Foram fabricados e usados dois conjuntos de 10 pastilhas de Al2O3 com densidades de 92% e 96%. Foi desenvolvida técnica ultrassônica por transmissão obtendo medidas do tempo de percurso de ondas ultrassônicas, longitudinais e transversais, usadas para a determinação das constantes elásticas do material. Equações relacionando a velocidade da onda ultrassônica ao módulo de elasticidade, módulo de cisalhamento e coeficiente de Poisson, permitiram obter essas constantes elásticas, que apresentaram excelente concordância com a literatura disponível para o Al2O3.