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.

Cryogenic Silicon Optical Reference Cavities

Thermodynamical fluctuations in temperature and position exist in every physical system, and show up as a fundamental noise limit whenever we choose to measure some quantity in a laboratory environment. Thermodynamical fluctuations in the position of the atoms in the dielectric coatings on the mirrors for optical cavities at the forefront of precision metrology (e.g., LIGO, the cavities which probe atomic transitions to define the second) are a current limiting noise source for these experiments, and anything which involves locking a laser to an optical cavity. These thermodynamic noise sources scale physical geometry of experiment, material properties (such as mechanical loss in our dielectric coatings), and temperature. The temperature scaling provides a natural motivation to move to lower temperatures, with a potential huge benefit for redesigning a room temperature experiment which is limited by thermal noise for cryogenic operation.

We design, build, and characterize a pair of linear Fabry-Perot cavities to explore limitations to ultra low noise laser stabilization experiments at cryogenic temperatures. We use silicon as the primary material for the cavity and mirrors, due to a zero crossing in its linear coefficient of thermal expansion (CTE) at 123 K, and other desirable material properties. We use silica tantala coatings, which are currently the best for making high finesse low noise cavities at room temperature. The material properties of these coating materials (which set the thermal noise levels) are relatively unknown at cryogenic temperatures, which motivates us to study them at these temperatures. We were not able to measure any thermal noise source with our experiment due to excess noise. In this work we analyze the design and performance of the cavities, and recommend a design shift from mid length cavities to short cavities in order to facilitate a direct measurement of cryogenic coating noise.

In addition, we measure the cavities (frequency dependent) photo-thermal response. This can help characterize thermooptic noise in the coatings, which is poorly understood at cryogenic temperatures. We also explore the feasibility of using the cavity to do macroscopic quantum optomechanics such as ground state cooling.

Spectral shaping of femtosecond pulses with a prism-waveguide coupler

We report a novel technique for spectral shaping of femtosecond pulses employing a prism-waveguide coupler (PWC). It is demonstrated that the PWC is capable of producing a frequency-dependent loss with greater attenuation at the peak of the spectrum profile of femtosecond pulses than in the wings, which is especially useful for compensation for gain narrowing in most chirped-pulse amplification laser systems.

Luminescence and Magnetic Properties of Two Three -Dimensional Terbium and Dysprosium MOFs Based on Azobenzene-4,4 '-Dicarboxylic Linker

We report the in situ formation of two novel metal-organic frameworks based on terbium and dysprosium ions using azobenzene-4,4-dicarboxylic acid (H(2)abd) as ligand, synthesized by soft hydrothermal routes. Both materials show isostructural three-dimensional networks with channels along a axis and display intense photoluminescence properties in the solid state at room temperature. Textural properties of the metal-organic frameworks (MOFs) have been fully characterized although no appreciable porosity was obtained. Magnetic properties of these materials were studied, highlighting the dysprosium material displays slightly frequency-dependent out of phase signals when measured under zero external field and under an applied field of 1000 Oe.

Trapped charge dynamics in a sol-gel based TiO(2) high- k gate dielectric silicon metal-oxide-semiconductor field effect transistor.

We have studied the response of a sol-gel based TiO(2), high k dielectric field effect transistor structure to microwave radiation. Under fixed bias conditions the transistor shows frequency dependent current fluctuations when exposed to continuous wave microwave radiation. Some of these fluctuations take the form of high Q resonances. The time dependent characteristics of these responses were studied by modulating the microwaves with a pulse signal. The measurements show that there is a shift in the centre frequency of these high Q resonances when the pulse time is varied. The measured lifetime of these resonances is high enough to be useful for non-classical information processing.

The myogenic automatism of the systemic heart of Octopus vulgaris (Cephalopoda: Coleoidea): evidence for localized stretch sensitivity and pacing activity

The localization of the stretch sensitivity and myogenic automatism in the systemic heart of Octopus vulgaris has been studied on an isolated preparation in which the ventricle was zoned by ligatures. Each region has been submitted to two different levels of internal hydrostatic pressure (1 and 2 kPa). Only the two atrio-ventricular regions were able to contract regularly when submitted to internal pressure, with a frequency dependent from the pressure value, while the ventricle-aortic region was insensitive to the stretching by internal pressure. This result supports the hypothesis that the automatism in this heart is localized. Electrocardiogram recordings from different areas of an isolated and perfused preparation of the systemic heart ventricle are also reported, which suggest that the electrical activity of the ventricle originates in two narrow areas near the atrio-ventricular valves.

Modelo simple para la permeabilidad dinámica de fluidos viscoelásticos

In the present work a simple form to obtain analytical expression for the dynamic permeability of Maxwellian fluids is presented. This expression gives the frequency dependent form of this dynamic permeability. In particular case, the analytic expression for the sinusoidal pressure pump fluid is illustrated in the configuration space. As an example of the feasibility of this expression the flow of human blood in a tube is presented finding that the human heart frequency has the same order that the frequencies where the dynamic permeability shows resonances. In order to make clear the above aspect of the dynamic permeability a model of pulsing pressure drops (gaussian like) are analyzed.

Terahertz time-domain spectroscopy characterization of vertically aligned carbon nanotube films

Terahertz time-domain spectroscopy measurements were made for vertically aligned multi-walled carbon nanotube (VACNT) films. We obtained the frequency dependent complex permittivity and conductivity (on the assumption that permeability μ = 1) of several samples exhibiting Drude behaviour for lossy metals. The obtained material properties of VACNT films provide information for potential microwave and terahertz applications. © 2011 Elsevier Ltd. All rights reserved.

Effects of nonuniform reactant stoichiometry on thermoacoustic instability in a lean-premixed gas turbine combustor

Detailed experimental investigations of the amplitude dependence of flame describing functions (FDF) were performed using a stratified swirl-stabilized combustor, in order to understand the combustion-acoustic interactions of CH4/air flames propagating into nonhomogeneous reactant stoichiometry. Phase-synchronized OH planar laser induced fluorescence (OH PLIF) measurements were used to investigate local reaction zone structures of forced flames. To determine the amplitude-and frequency-dependent forced flame response, simultaneous measurements of inlet velocity and heat release rate oscillations were made using a constant temperature anemometer and photomultiplier tubes with narrow-band OH*/CH* interference filters. The measurements were made over a wide range of stratification ratios, including inner stream enrichment ( θ o>θ i) and outer stream enrichment ( θ o>θ i)) conditions, and compared to the baseline condition of spatially and temporally homogeneous cases ( θ o=θ i)). Results show that for the inlet conditions investigated, fuel stratification has a significant influence on local and global flame structures of unforced and forced flames. Under stratified conditions, length scales of local contours were found to be much larger than the homogeneous case due to high kinematic viscosities associated with high temperature. Stratification has a remarkable effect on flame-vortex interactions when the flame is subjected to high-amplitude acoustic forcing, leading to different evolution patterns of FDF (amplitude and disturbance convective time) in response to the amplitude of the imposed inlet velocity oscillation. The present experimental investigation reveals that intentional stratification has the potential to eliminate or suppress the occurrence of detrimental combustion instability problems in lean-premixed gas turbine combustion systems. © 2012 Copyright Taylor and Francis Group, LLC.

Positive Correlations in Tunneling through coupled Quantum Dots

Due to the Fermi-Dirac statistics of electrons the temporal correlations of tunneling events in a double barrier setup are typically negative. Here, we investigate the shot noise behavior of a system of two capacitively coupled quantum dot states by means of a Master equation model. In an asymmetric setup positive correlations in the tunneling current can arise due to the bunching of tunneling events. The underlying mechanism will be discussed in detail in terms of the current-current correlation function and the frequency-dependent Fano factor.

Friction-induced vibration: Model development and comparison with large-scale experimental tests

This paper presents a comparison between theoretical predictions and experimental results from a pin-on-disc test rig exploring friction-induced vibration. The model is based on a linear stability analysis of two systems coupled by sliding contact at a single point. Predictions are compared with a large volume of measured squeal initiations that have been post-processed to extract growth rates and frequencies at the onset of squeal. Initial tests reveal the importance of including both finite contact stiffness and a velocity-dependent dynamic model for friction, giving predictions that accounted for nearly all major clusters of squeal initiations from 0 to 5 kHz. However, a large number of initiations occurred at disc mode frequencies that were not predicted with the same parameters. These frequencies proved remarkably difficult to destabilise, requiring an implausibly high coefficient of friction. An attempt has been made to estimate the dynamic friction behaviour directly from the squeal initiation data, revealing complex-valued frequency-dependent parameters for a new model of linearised dynamic friction. These new parameters readily destabilised the disc modes and provided a consistent model that could account for virtually all initiations from 0 to 15 kHz. The results suggest that instability thresholds for a wide range of squeal-type behaviour can be predicted, but they highlight the central importance of a correct understanding and accurate description of dynamic friction at the sliding interface. © 2013 Elsevier Ltd. All rights reserved.

Dynamic models of piled foundations

The vibration behavior of piled foundations is an important consideration in fields such as earthquake engineering, construction, machine-foundation design, offshore structures, nuclear energy, and road and rail development. This paper presents a review of the past 40 years' literature on modeling the frequency-dependent behavior of pile foundations. Beginning with the earliest model of a single pile, adapted from those for embedded footings, it charts the development of the four pile-modeling techniques: the "dynamic Winkler-foundation" approach that uses springs to represent the effect of the soil; elasticcontinuum-type formulations involving the analytical solutions for displacements due to a subsurface disk, cylinder, or other element; boundary element methods; and dynamic finite-element formulations with special nonreflecting boundaries. The modeling of pile groups involves accounting for pile-soil-pile interactions, and four such methods exist: interaction factors; complete pile models; the equivalent pier method; and periodic structure theory. Approaches for validating pile models are also explored. Copyright © 2013 by ASME.

Quantum Confinement and Electronic Properties of Rutile TiO2 Nanowires

The quantum confinement effect, electronic properties, and optical properties of TiO2 nanowires in rutile structure are investigated via first-principles calculations. We calculate the size- and shape-dependent band gap of the nanowires and fit the results with the function E-g = E-g(bulk) + beta/d(alpha). We find that the quantum confinement effect becomes significant for d < 25 angstrom, and a notable anisotropy exists that arises from the anisotropy of the effective masses. We also evaluate the imaginary part of the frequency-dependent dielectric function [epsilon(2)(omega)] within the electric-dipole approximation, for both the polarization parallel [epsilon(parallel to)(2)(omega)] and the perpendicular [epsilon 1/2(omega)] to the axial (c) direction. The band structure of the nanowires is calculated, with which the fine structure of epsilon(parallel to)(2)(omega) has been analyzed.

Resonant Raman scattering of a-SiNx : H

Micro-Raman measurements were carried out to investigate the microstructure of amorphous silicon-nitrogen alloy (a-SiNx:H) samples with different N contents prepared by plasma enhanced chemical vapor deposition (PECVD). Resonant Raman effect was discovered by using 647.1- and 514.5-nm excitation wavelengths. The frequency of TO mode downshifts with increasing photon energy without varying its width, while LO mode expands to a great extent. The frequency-dependent shift of TO band is explained by heterogeneous structure model and quantum confinement model, and the width expansion of LO mode may be related to the overlapping of LA and LO bands. (C) 2001 Elsevier Science B.V. All rights reserved.

A monometallic tri-spin single-molecule magnet based on rare earth radicals

A mononuclear tri-spin single-molecule magnet based on the rare earth radical [Tb(hfac)(3)(NITPhOEt)(2)] (NITPhOEt = 4'-ethoxy-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized, structurally characterized and the alternating current signals show a slow relaxation of magnetization and frequency-dependent signals.