A study of the vacuum gamma-radiolysis of two aromatic polyimide fluoropolymers containing phenylphosphine oxide

The vacuum gamma -radiolysis of two fluorinated polyimides containing phenylphosphine oxide units, TOR-RC and TOR-RC ODPA, have been studied at 77 K and 300 K. The phenyl phosphine oxide units provide protection of the polymers towards oxidation by oxygen atoms and the bulky fluoromethyl groups reduce the colouration of the polymers by limiting donor-acceptor complex formation through the aromatic units. At 77 K the radicals formed were identified to be a mixture of neutral radicals (60%) and anion radicals. At 300 K only neutral radicals were found. The G-values for radical formation were found to be 0.50 and 0.42 at 77 K and 0.051 and 0.052 at 300 K for TOR-RC and TOR-RC ODPA, respectively. Little change was observed in the visible spectra of the polyimides following vacuum radiolysis at 300 K up to a dose of 3.3 MGy, and the polymers were shown to undergo net cross linking with a gel dose of 0.45 MGy.

Synthesis of [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)] (PF6)(2), a hydroxo-bridged copper(II) complex of N,N '-dimethyl-1-thia-4,7-diazacyclononane (Me-2[9]aneN(2)S). X-ray structural analysis, magnetic susceptibility, EPR and visible spectroscopy

The bis(mu-hydroxo) complex [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)](PF6)(2) (Me-2[9]aneN(2)S = N,N'-dimethyl-1-thia-4,7-diazacyclononane) results after reaction of [Cu(Me-2[9]aneN(2)S)(MeCN)] (PF6) with dioxygen at -78 degrees C in acetonitrile. The complex has been characterized by X-ray crystallography: orthorhombic, space group Pnma, with a 18.710(3), b 16.758(2), c 9.593(2) Angstrom, and Z = 4. The structure refined to a final R value of 0.051. The complex contains two copper(II) ions bridged by two hydroxo groups with Cu ... Cu 2.866(1) Angstrom. The solid-state magnetic susceptibility study reveals ferromagnetic coupling, the fitting parameters being J = +46+/-5 cm(-1), g = 2.01+/-0.01 and theta = -0.58+/-0.03 K. The frozen-solution e.p.r. spectrum in dimethyl sulfoxide is characteristic of a monomeric copper(II) ion (g(parallel to) 2.300, g(perpendicular to) 2.063; A(parallel to) 156.2 x 10(-4) cm(-1), A(perpendicular to) 9.0 x 10(-4) cm(-1)) with an N2O2 donor set. Thioether coordination to the copper(II) in solution is supported by the presence of an intense absorption assigned to a sigma(S)-->Cu-II LMCT transition at c. 34000 cm(-1). The single-crystal spectrum of [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)] (PF6)(2) (273 K) reveals d-->d transitions at 14500 and 18300 cm(-1) and a weak pi(S)-->Cu-II charge-transfer band at approximately 25000 cm(-1).

Separating fluorescent species of aqueous PbS semiconductor nanocrystals using micro-emulsions

Colloidal PbS nanocrystals over-coated with CdS are prepared in aqueous solutions and exhibit strong photoluminescence with two distinct peaks in the visible regime. A photoluminescence peak is observed at 640 nm, which is attributed to the band edge recombination in the PbS nanocrystals, and another peak at 510 nm, which is above the band edge of the PbS nanocrystals. The two PL peaks are isolated by extracting separate species of nanocrystal based upon their surface morphology. Micro-emulsions of hexane:PVA are used to remove the species containing the PL peak at 640 nm from the solution, leaving a singular peak at 510 nm. We show conclusively that the double-peaked structure observed in the photoluminescence spectra of PbS nanocrystals over-coated with CdS is due to the presence of two distinctly different nanocrystal species.

Radiative Relaxation Quantum Yields for Synthetic Eumelanin

We report absolute values for the radiative relaxation quantum yield of synthetic eumelanin as a function of excitation energy. These values were determined by correcting for pump beam attenuation and emission reabsorption in both eumelanin samples and fluorescein standards over a large range of concentrations. Our results confirm that eumelanins are capable of dissipating >99.9% of absorbed UV and visible radiation through nonradiative means. Furthermore, we have found that the radiative quantum yield of synthetic eumelanin is excitation energy dependent. This observation is supported by corrected emission spectra, which also show a clear dependence of both peak position and peak width on excitation energy. Our findings indicate that photoluminescence emission in eumelanins is derived from ensembles of small chemically distinct oligomeric units that can be selectively pumped. This hypothesis lends support to the theory that the basic structural unit of eumelanin is oligomeric rather than heteropolymeric.

Algebraic Bethe ansatz method for the exact calculation of energy spectra and form factors: applications to models of Bose-Einstein condensates and metallic nanograins

In this review we demonstrate how the algebraic Bethe ansatz is used for the calculation of the-energy spectra and form factors (operator matrix elements in the basis of Hamiltonian eigenstates) in exactly solvable quantum systems. As examples we apply the theory to several models of current interest in the study of Bose-Einstein condensates, which have been successfully created using ultracold dilute atomic gases. The first model we introduce describes Josephson tunnelling between two coupled Bose-Einstein condensates. It can be used not only for the study of tunnelling between condensates of atomic gases, but for solid state Josephson junctions and coupled Cooper pair boxes. The theory is also applicable to models of atomic-molecular Bose-Einstein condensates, with two examples given and analysed. Additionally, these same two models are relevant to studies in quantum optics; Finally, we discuss the model of Bardeen, Cooper and Schrieffer in this framework, which is appropriate for systems of ultracold fermionic atomic gases, as well as being applicable for the description of superconducting correlations in metallic grains with nanoscale dimensions.; In applying all the above models to. physical situations, the need for an exact analysis of small-scale systems is established due to large quantum fluctuations which render mean-field approaches inaccurate.

XSophe-Sophe-XeprView (R). A computer simulation software suite (v. 1.1.3) for the analysis of continuous wave EPR spectra

The XSophe-Sophe-XeprView((R)) computer simulation software suite enables scientists to easily determine spin Hamiltonian parameters from isotropic, randomly oriented and single crystal continuous wave electron paramagnetic resonance (CW EPR) spectra from radicals and isolated paramagnetic metal ion centers or clusters found in metalloproteins, chemical systems and materials science. XSophe provides an X-windows graphical user interface to the Sophe programme and allows: creation of multiple input files, local and remote execution of Sophe, the display of sophelog (output from Sophe) and input parameters/files. Sophe is a sophisticated computer simulation software programme employing a number of innovative technologies including; the Sydney OPera HousE (SOPHE) partition and interpolation schemes, a field segmentation algorithm, the mosaic misorientation linewidth model, parallelization and spectral optimisation. In conjunction with the SOPHE partition scheme and the field segmentation algorithm, the SOPHE interpolation scheme and the mosaic misorientation linewidth model greatly increase the speed of simulations for most spin systems. Employing brute force matrix diagonalization in the simulation of an EPR spectrum from a high spin Cr(III) complex with the spin Hamiltonian parameters g(e) = 2.00, D = 0.10 cm(-1), E/D = 0.25, A(x) = 120.0, A(y) = 120.0, A(z) = 240.0 x 10(-4) cm(-1) requires a SOPHE grid size of N = 400 (to produce a good signal to noise ratio) and takes 229.47 s. In contrast the use of either the SOPHE interpolation scheme or the mosaic misorientation linewidth model requires a SOPHE grid size of only N = 18 and takes 44.08 and 0.79 s, respectively. Results from Sophe are transferred via the Common Object Request Broker Architecture (CORBA) to XSophe and subsequently to XeprView((R)) where the simulated CW EPR spectra (1D and 2D) can be compared to the experimental spectra. Energy level diagrams, transition roadmaps and transition surfaces aid the interpretation of complicated randomly oriented CW EPR spectra and can be viewed with a web browser and an OpenInventor scene graph viewer.

Fast Structure-Based Assignment of 15N HSQC Spectra of Selectively 15N-Labeled Paramagnetic Proteins

A novel strategy for fast NMR resonance assignment of N-15 HSQC spectra of proteins is presented. It requires the structure coordinates of the protein, a paramagnetic center, and one or more residue-selectively N-15-labeled samples. Comparison of sensitive undecoupled N-15 HSQC spectra recorded of paramagnetic and diamagnetic samples yields data for every cross-peak on pseudocontact shift, paramagnetic relaxation enhancement, cross-correlation between Curie-spin and dipole-dipole relaxation, and residual dipolar coupling. Comparison of these four different paramagnetic quantities with predictions from the three-dimensional structure simultaneously yields the resonance assignment and the anisotropy of the susceptibility tensor of the paramagnetic center. The method is demonstrated with the 30 kDa complex between the N-terminal domain of the epsilon subunit and the theta subunit of Escherichia Coll DNA polymerase III. The program PLATYPUS was developed to perform the assignment, provide a measure of reliability of the assignment, and determine the susceptibility tensor anisotropy.

Anomalous fluorescence spectra in an extremely weak, broadband squeezed vacuum under monochromatic and bichromatic excitation

We show that a two-level atom interacting with an extremely weak squeezed vacuum can display resonance fluorescence spectra that are qualitatively different to those that can be obtained using fields with a classical analogue. We consider first the free space situation with monochromatic excitation, and then discuss a bichromatically driven two-level atom in a cavity as a practical scenario for experimentally detecting the anomalous features predicted. We show that in the bad cavity limit, the anomalous spectral features appear for a weak squeezed vacuum and large frequency differences of the bichromatic field, conditions which are easily accessible in laboratories. The advantage of bichromatic, as opposed to monochromatic, excitation is that there is no coherent scattering at line centre which could obscure the observations. A scaling law is derived, N similar to Omega(4) which relates the squeezed photon number to the Rabi frequency at which the anomalous features appear. (C) 1998 Elsevier Science B.V.

Analytical solution for the Mollow and Autler-Townes probe absorption spectra of a three-level atom in a squeezed vacuum

The Mellow and Autler-Townes probe absorption spectra of a three-level atom in a cascade configuration with the lower transition coherently driven and also coupled to a narrow bandwidth squeezed-vacuum field are studied. Analytical studies of the modifications caused by the finite squeezed-vacuum bandwidth to the spectra are made for the case when the Rabi frequency of the driving field is much larger than the natural linewidth. The squeezed vacuum center frequency and the driving laser frequency are assumed equal. We show that the spectral features depend on the bandwidth of a squeezed vacuum field and whether the sources of the squeezing field are degenerate (DPA) or nondegenerate (NDPA) parametric amplifiers. In a broadband or narrow bandwidth squeezed vacuum generated by a NDPA, the central component of the Mellow spectrum can be significantly narrower than that in the normal vacuum. When the source of the squeezed vacuum is a DPA, the central feature is insensitive to squeezing. The Rabi sidebands, however, can be significantly narrowed only in the squeezed vacuum produced by the DPA. The two lines of the Autler-Townes absorption spectrum can be narrowed only in a narrow bandwidth squeezed vacuum, whereas they are independent of the phase and are always broadened in a broadband squeezed vacuum.

Sharp vibronic spectra of Cu(II) doped Cs2ZrCl6

The low temperature electronic spectrum of Cu(II) doped Cs2ZrCl6 is reported. It is found that Cu(II) is incorporated as the square planar copper tetrachloride ion, CuCl42-, which substitutes at the Zr(IV) site in the Cs2ZrCl6 lattice. There is a complete absence of axial coordination. The optical spectrum shows vibronic structure with peak widths as small as 8 cm(-1), far narrower than previously seen for this ion. The energy of the observed transitions and the Franck-Condon intensity pattern suggest that there is a substantial relaxation of the host lattice about the impurity ion. The relative intensity of the magnetic dipole component of the bands appears to be considerably greater than for pure copper(II) compounds containing the CuCl42- ion. (C) 1998 Elsevier Science B.V. All rights reserved.

A wavelet visible difference predictor

In this paper, we describe a model of the human visual system (HVS) based on the wavelet transform. This model is largely based on a previously proposed model, but has a number of modifications that make it more amenable to potential integration into a wavelet based image compression scheme. These modifications include the use of a separable wavelet transform instead of the cortex transform, the application of a wavelet contrast sensitivity function (CSP), and a simplified definition of subband contrast that allows us to predict noise visibility directly from wavelet coefficients. Initially, we outline the luminance, frequency, and masking sensitivities of the HVS and discuss how these can be incorporated into the wavelet transform. We then outline a number of limitations of the wavelet transform as a model of the HVS, namely the lack of translational invariance and poor orientation sensitivity. In order to investigate the efficacy of this wavelet based model, a wavelet visible difference predictor (WVDP) is described. The WVDP is then used to predict visible differences between an original and compressed (or noisy) image. Results are presented to emphasize the limitations of commonly used measures of image quality and to demonstrate the performance of the WVDP, The paper concludes with suggestions on bow the WVDP can be used to determine a visually optimal quantization strategy for wavelet coefficients and produce a quantitative measure of image quality.

The spectra of red quasars

We measure the spectral properties of a representative sub-sample of 187 quasars, drawn from the Parkes Half-Jansky, Flat-radio-spectrum Sample (PHFS). Quasars with a wide range of rest-frame optical/UV continuum slopes are included in the analysis: their colours range over 2 < B-K < 7. We present composite spectra of red and blue sub-samples of the PHFS quasars. and tabulate their emission line properties. The median Hbeta and [0 111] emission line equivalent widths of the red quasar sub-sample are a factor of ten weaker than those of the blue quasar sub-sample. No significant differences are seen between the equivalent width distributions of the C IV, C III] and Mg 11 lines. Both the colours and the emission line equivalent widths of the red quasars can be explained by the addition of a featureless red synchrotron continuum component to an otherwise normal blue quasar spectrum. The red synchrotron component must have a spectrum at least as red as a power-law of the form F-nu proportional to nu(-2.8). The relative strengths of the blue and red components span two orders of magnitude at rest-frame 500 nm. The blue component is weaker relative to the red component in low optical luminosity sources. This suggests that the fraction of accretion energy going into optical emission from the jet is greater in low luminosity quasars. This correlation between colour and luminosity may be of use in cosmological distance scale work. This synchrotron model does not, however, fit similar to10% of the quasars, which have both red colours and high equivalent width emission lines. We hypothesise that these red, strong-lined quasars have intrinsically weak Big Blue Bumps. There is no discontinuity in spectral properties between the BL Lac objects in our sample and the other quasars. BL Lac objects appear to be the red, low equivalent width tail of a continuous distribution. The synchrotron emission component only dominates the spectrum at longer wavelengths, so existing BL Lac surveys will be biased against high redshift objects. This will affect measurements of BL Lac evolution. The blue PHFS quasars have significantly higher equivalent width C IV, Hbeta and [0 111] emission than a matched sample of optically selected QSOs.

Resonance fluorescence and Autler-Townes spectra of a two-level atom driven by two fields of equal frequencies

We study the effects of driving a two-level atom by two intense field modes that have equal frequencies but are otherwise distinguishable; the intensity of one mode is also assumed to be greater than that of the other. We calculate first the dressed states of the system, and then its resonance fluorescence and Autler-Townes absorption spectra. We find that the energy spectrum of the doubly dressed atom consists of a ladder of doublet continua. These continua manifest themselves in the fluorescence spectrum, where they produce continua at the positions of the Mellow sideband frequencies omega(L)+/-2 Omega of the strong field, and in the Autler-Townes absorption spectrum, which becomes a two-continuum doublet.

Spin-orbit mixing and nephelauxetic effects in the electronic spectra of nickel(II)-encapsulating complexes involving nitrogen and sulfur donors

A study of spin-orbit mixing and nephelauxetic effects in the electronic spectra of nickel(II)-encapsulating complexes involving mixed nitrogen and sulfur donors is reported. As the number of sulfur donors is systematically varied through the series [Ni(N6-xSx)](2+) (x = 0-6), the spin-forbidden (3)A(2)g --> E-1(g) and (3)A(2g) --> (1)A(1g) transitions undergo a considerable reduction in energy whereas the spin-allowed transitions are relatively unchanged. The [Ni(diAMN(6)sar)](2+) and [Ni(AMN(5)Ssar)](2+) complexes exhibit an unusual band shape for the (3)A(2g) --> T-3(2g) transition which is shown to arise from spin-orbit mixing of the E spin-orbit levels associated with the E-1(g) and T-3(2g) states. A significant differential nephelauxetic effect also arises from the covalency differences between the t(2g) and e(g) orbitals with the result that no single set of Racah B and C interelectron repulsion parameters adequately fit the observed spectra. Using a differential covalency ligand-field model, the spectral transitions are successfully reproduced with three independent variables corresponding to 10Dq and the covalency parameters f(t) and f(e), associated with the t(2g) and e(g) orbitals, respectively. The small decrease in f(t) from unity is largely attributed to central-field covalency effects whereas the dramatic reduction in f(e) with increasing number of sulfur donors is a direct consequence of the increased metal-ligand covalency associated with the sulfur donors. Covalency differences between the t(2g) and e(g) orbitals also result in larger 10Dq values than those obtained simply from the energy of the (3)A(2g) --> T-3(2g) spin-allowed transition.