Family of Mixed-Valence Oxovanadium(IV/V) Dinuclear Entities Incorporating N4O3-Coordinating Heptadentate Ligands: Synthesis, Structure, and EPR Spectra

Dinuclear ((VVV)-V-IV) oxophenoxovanadates of general formula [V2O3L] have been synthesized in excellent yields by reacting bis(acetylacetonato)oxovanadium(IV) with H3L in a 2:1 ratio in acetone under an N-2 atmosphere. Here L3- is the deprotonated form of 2,6-bis[{{(2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L1), 2,6-bis[{{(5-methyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L2) 2,6-bis[ {{(5-tert-butyl-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenoI (H3L3), 2,6-bis[{{(5-chloro-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L4) , 2,6-bis[{{(5-bromo-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L5), or 2,6-bis[{{(5-methoxy-2-hydroxybenzyl)(N',N'-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol (H3L6). In [V2O3L1], both the metal atoms have distorted octahedral geometry. The relative disposition of two terminal V=O groups in the complex is essentially cis. The O=V...V=O torsion angle is 24.6(2)degrees. The V-O-oxo-V and V-O-phenoxo-V angles are 117.5(4) and 93.4(3)degrees, respectively. The V...V bond distance is 3.173(5) Angstrom. X-ray crystallography, IR, UV-vis, and H-1 and V-51 NMR measurements show that the mixed-valence complexes contain two indistinguishable vanadium atoms (type 111). The thermal ellipsoids of O2, O4, C10, C14, and C15 also suggests a type III complex in the solid state. EPR spectra of solid complexes at 77 K display a single line indicating the localization of the odd electron (3d(xy)(1)). Valence localization at 77 K is also consistent with the V-51 hyperfine structure of the axial EPR spectra (3d(xy)(1) ground state) of the complexes in frozen (77 K) dichloromethane solution: S = 1/2, g(parallel to) similar to 1.94, g(perpendicular to) similar to 1.98, A(parallel to) similar to 166 x 10(-4) cm(-1), and A(perpendicular to) similar to 68 x 10(-4) cm(-1). In contrast isotropic room-temperature solution spectra of the family have 15 hyperfine lines (g(iso) similar to 1.974 and A(iso) similar to 50 x 10(-4) cm(-1)) revealing that the unpaired electron is delocalized between the metal centers. Crystal data for the [V2O3L1].CH2Cl2 complex are as follows: chemical formula, C32H43O6N4C12V2; crystal system, monoclinic; space group, C2/c; a = 18.461(4), b = 17.230(3), c = 13.700(3) Angstrom; beta = 117.88(3)degrees; Z = 8.

A novel fractional sampling offset estimation in an OFDM system

The Orthogonal Frequency Division Multiplexing (OFDM) is a form of Multi-Carrier Modulation where the data stream is transmitted over a number of carriers which are orthogonal to each other i.e. the carrier spacing is selected such that each carrier is located at the zeroes of all other carriers in the spectral domain. This paper proposes a new novel sampling offset estimation algorithm for an OFDM system in order to receive the OFDM data symbols error-free over the noisy channel at the receiver and to achieve fine timing synchronization between the transmitter and the receiver. The performance of this algorithm has been studied in AWGN, ADSL and SUI channels successfully.

A Study of Practical Biological Phantoms with Simple Instrumentation for Electrical Impedance Tomography (EIT)

16-electrode phantoms are developed and studied with a simple instrumentation developed for Electrical Impedance Tomography. An analog instrumentation is developed with a sinusoidal current generator and signal conditioner circuit. Current generator is developed withmodified Howland constant current source fed by a voltage controlled oscillator and the signal conditioner circuit consisting of an instrumentation amplifier and a narrow band pass filter. Electronic hardware is connected to the electrodes through a DIP switch based multiplexer module. Phantoms with different electrode size and position are developed and the EIT forward problem is studied using the forward solver. A low frequency low magnitude sinusoidal current is injected to the surface electrodes surrounding the phantom boundary and the differential potential is measured by a digital multimeter. Comparing measured potential with the simulated data it is intended to reduce the measurement error and an optimum phantom geometry is suggested. Result shows that the common mode electrode reduces the common mode error of the EIT electronics and reduces the error potential in the measured data. Differential potential is reduced up to 67 mV at the voltage electrode pair opposite to the current electrodes. Offset potential is measured and subtracted from the measured data for further correction. It is noticed that the potential data pattern depends on the electrode width and the optimum electrode width is suggested. It is also observed that measured potential becomes acceptable with a 20 mm solution column above and below the electrode array level.

Infrared spectra of substituted benzoyl chlorides and benzoyl bromides. Explanation of the anomalous carbonyl band-splittings

Infrared spectra of substituted benzoyl chlorides and benzoyl bromides have been studied. The extent of splitting of the carbonyl band in benzoyl chlorides varies with substitution. While benzoyl bromide shows the carbonyl band as a single peak, para-nitrobenzoyl bromide shows a doublet. The results are interpreted in terms of intramolecular vibration effects (Fermi resonance). The intense band in the 860–880 cm−1 region in benzoyl chloride and benzoyl bromide has been assigned to the Ph-C stretching vibration.

Response of nonlinear systems to narrow-band excitation

The hardening cubic spring oscillator is studied under narrow-band gaussian excitation. Equivalent linearization leads to multiple steady states. The realizability of the solution is discussed through stochastic stability analysis. Theoretical results are supported by numerical simulation.

Modified linear prediction method for directions of arrival estimation of narrow-band plane waves

A modified linear prediction (MLP) method is proposed in which the reference sensor is optimally located on the extended line of the array. The criterion of optimality is the minimization of the prediction error power, where the prediction error is defined as the difference between the reference sensor and the weighted array outputs. It is shown that the L2-norm of the least-squares array weights attains a minimum value for the optimum spacing of the reference sensor, subject to some soft constraint on signal-to-noise ratio (SNR). How this minimum norm property can be used for finding the optimum spacing of the reference sensor is described. The performance of the MLP method is studied and compared with that of the linear prediction (LP) method using resolution, detection bias, and variance as the performance measures. The study reveals that the MLP method performs much better than the LP technique.

External Bias Dependent Direct To Indirect Band Gap Transition in Graphene Nanoribbon

In this work, using self-consistent tight-binding calculations. for the first time, we show that a direct to indirect band gap transition is possible in an armchair graphene nanoribbon by the application of an external bias along the width of the ribbon, opening up the possibility of new device applications. With the help of the Dirac equation, we qualitatively explain this band gap transition using the asymmetry in the spatial distribution of the perturbation potential produced inside the nanoribbon by the external bias. This is followed by the verification of the band gap trends with a numerical technique using Magnus expansion of matrix exponentials. Finally, we show that the carrier effective masses possess tunable sharp characters in the vicinity of the band gap transition points.

Stability of CU(2)Ln(2)O(5) compounds - Comparison, assessment and systematics

Phase diagram studies show that at ambient pressure only one ternary oxide, Cu(2)Ln(2)O(5), is stable in the ternary systems Cu-Ln-O (Ln = Tb, Dy, Ho, Er, Tm, Yb, Lu) at high temperatures. The crystal structure of Cu(2)Ln(2)O(5) can be described as a zig-zag arrangement of one-dimensional Cu2O5 chains parallel to-the a-axis with Ln atoms occupying distorted octahedral sites between these chains. Four sets of emf measurements on Gibbs energy of formation of Cu(2)Ln(2)O(5) (Ln = Tb, Dy, Ho, Er, Tm, Yb, Lu; Y) from component binary oxides and one set of high-temperature solution calorimetric data on enthalpy of formation have been reported in the literature. Except for Cu2Y2O5, the measured values for the Gibbs energies of formation of all other Cu(2)Ln(2)O(5) compounds fall in a narrow band (+/-1 kJ mol(-1)) and indicate a regular increase in stability with decreasing ionic radius of the lanthanide ion. The values for the second law enthalpy of formation, derived from the temperature dependence of emf obtained in different studies, show larger differences, as high as 25 kJ mol(-1) for Cu2Tm2O5. Though associated with an uncertainty of +/-4 kJ mol(-1), the calorimetric measurements help to identify the best set of emf data. The trends in thermodynamic data correlate well with the global instability index (GII) based on the overall deviation from the valence sum rule. Low values for the index calculated from crystallographic information indicate higher stability. Higher values are indicative of the larger stress in the structure.

Broad-Band Coupling of High-Q Resonant Loads

Considering the method of broad-band coupling a series resonant RLC load to a resistive source using a uniform quarter-wave transmission-line inverter, it is shown that the 3-dB bandwidth of the network insertion loss reckoned with respect to a 0-dB loss attains a maximum for a particular value of the center frequency insertion loss in the range 0-3 dB. The center frequency Ioss and the corresponding value of the maximum 3-dB bandwidth are calculated for various loads and the results graphically presented.

Transition metal oxide perovskites by photoelectron and x-ray absorption spectroscopy

X-ray and ultraviolet photoelectron spectroscopy as well as x-ray absorption spectroscopy have been employed to investigate transition metal oxide perovskites of the general formula ABOs (A=La or rare-earth ion, B=trivalent transition metalion). Systematics in the core levels and in the valence bands in the series of LaBOa compounds have been discussed. Lanthanum chemical shifts in the x-ray absorption spectra in this series show interesting trends. Photoelectron spectra of the solid solutions, LaNil_x Coxes, LaNix_x FexO8 and LaFel_x Coxes show that the rigid band model is applicable to these systems. It is shown that x-ray photoelectron spectroscopy can be employed to identify multiple oxidation states of transition metal ions in oxide perovskites.

Systematic Organic UV Photoelectron Spectroscopy

Photoelectron spectroscopy (PES) provides valuable information on the ionization energies of atoms and molecules. The ionization energy (IE) is given by the relation.hv = IE + T where hv is t h e energy of the radiation and T i s the kinetic energy of the electron. The IEs are directly related to the orbital energies (Koopmans' theorem). By employing UV radiation (HeI. 21.2 eV. or HeII. 40.8 eV). extensive data on the ionization of valence electrons in organic molecules have been obtained in recent years. These studies of UV photoelectron spectroscopy. originated by Turner, have provided a direct probe into the energy levels of organic molecules. Molecular orbital calculations of various degrees of sophistication are generally employed to make assignments of the PES bands. Analysis of the vibrational structure of PES bands has not only provided structural information on the molecular ions, but has also been of value in band assignments. Dewar and co-workers [1, 2) presented summaries of available PES data on organic molecules in 1969 and 1970. Turner et al. [3] published a handbook of Hel spectra of organic molecules in 1970. Since then, a few books [4-7] discussing the principles and applications of UV photoelectron spectroscopy have appeared of which special mention should be made of the recent article by Heilbronner and Maier [7]. There has, however, been no comprehensive review of the vast amount of data on the UV-PES of organic molecules published in the literature since 1970.

Pes study of spin-state transitions in d6 transition metal complexes and oxides

Transitions from the low-to the high-spin state in Fe2+ and Co3+ compounds have been examined by X-ray and UV photoelectron spectroscopy. It has been shown that the core-level bands in XPES, in particular the metal 3s band, as well as the valence bands, are diagnosis in the study of spin-state transitions.

Q-band beam waveguide

A report of the design, development ana periom~ance characteristics of a Q-band (8 nim) confoal. mned, aielectric lens beam waveguide is presented.

Q-Band beam wave-guide

Consideration is given to a 25-foot long Q-band (8 mm) confocal, zoned dielectric lens beam waveguide. Numerical expressions for the axial and radial fields are presented. The experimental set-up consisted of uniformly spaced zoned dielectric lenses, a transmitting horn and a receiving horn. It was found that: (1) the wave beam is reiterated when confocal, zoned dielectric lenses act as phase transformers in place of smooth surfaced transformers in beam waveguides; (2) the axial field is oscillatory near the source and the oscillation persists for about 25 cm from the source; (3) the oscillation disappears after one lens is used; (4) higher order modes with higher attenuation rates die out faster than fundamental modes; (5) phase transformers do not alter beam modes; (6) without any lens the beam cross-section broadens significantly in the Z-direction; (7) with one lens the beam exhibits the reiteration phenomenon; and (8) inserting a second lens on the axial and cross-sectional field distribution shows further the reiteration principle.