Standing and travelling waves in the shallow-water circular hydraulic jump

A wave equation for a time-dependent perturbation about the steady shallow-water solution emulates the metric an acoustic white hole, even upon the incorporation of nonlinearity in the lowest order. A standing wave in the sub-critical region of the flow is stabilised by viscosity, and the resulting time scale for the amplitude decay helps in providing a scaling argument for the formation of the hydraulic jump. A standing wave in the super-critical region, on the other hand, displays an unstable character, which, although somewhat mitigated by viscosity, needs nonlinear effects to be saturated. A travelling wave moving upstream from the sub-critical region, destabilises the flow in the vicinity of the jump, for which experimental support has been given.     

A universally applicable composite modulated structure approach to ordered BaxMyTi8−yO16 hollandite-type solid solutions

A wide range of barium titanate hollandites of the form (M=Zn, Co, Mg, Fe and Mn) and (M=Fe) with nominal x ranging from 1.0 to 1.4 have been synthesized and examined to investigate the solid solution range and the nature of the ordering of the Ba ions. Electron diffraction studies confirm that the barium titanate hollandites are composite modulated single phase solid solutions made up of mutually incommensurable (along b) framework and Ba ion sub-structures. The overall superspace group symmetry was found to be I′2/m(0,,0)1. The symbol I′ here refers to the superspace centering operation (see below). Both the framework and the Ba sub-structures have the same I2/m average structure space group symmetry. The solid solution ranges for the hollandites were calculated from the positions of well-defined superlattice peaks in X-ray diffraction patterns. The effect of cooling rate on Ba ion ordering is also examined.     

A correlation study of small silver clusters

The formalisms of many body perturbation theory and coupled cluster theory have been used to study the electronic and geometric structures of neutral, cationic, and anionic small silver clusters. Hay-Wadt relativistic effective core potentials replacing the twenty-eight core electrons and a Gaussian basis set have been used. Topologically different clusters and clusters belonging to different symmetry groups have been identified and studied in detail. Full geometry optimizations have been carried out at four different correlated levels of theories. Ionization potentials, electron affinities, and fragmentation energies of the optimized clusters have been compared with other experimental and theoretical results available in the literature. No convergence problems are encountered at the various levels of correlated theories. This is noteworthy since it has been claimed in the literature that for d elements the MP series does not converge very well. Received 16 April 2002 / Received in final form 12 September 2002 Published online 21 January 2003 RID="a" ID="a"e-mail: akr@uta.edu     

Frequency-domain Hadamard spectroscopy

A new technique is proposed for multichannel excitation and detection of NMR signals in the frequency domain, an alternative to the widely used pulse-excited Fourier transform method. An extensive array of N radiofrequency irradiation channels covers the spectrum of interest. A selective radiofrequency pulse sequence is applied to each channel, generating a steady-state NMR response acquired one-point-at-a-time in the intervals between pulses. The excitation pattern is repeated N times, phase-encoded according to a Hadamard matrix, and the corresponding N composite responses are decoded by reference to the same matrix. This multiplex technique offers the same sensitivity advantage as conventional Fourier transform spectroscopy. The irradiation pattern may be tailored to concentrate on interesting spectral regions, to facilitate homonuclear double resonance, or to avoid exciting strong solvent peaks. As no free induction decay is involved, the new method avoids problems of pulse breakthrough or lineshape distortion by premature termination of the time-domain signal.     

Two-dimensional Hadamard spectroscopy

Direct frequency-domain excitation of NMR with an array of different radiofrequencies has been used to speed up two-dimensional NMR experiments by a large factor. Multiplex excitation in the F(1) frequency dimension is restricted to the signal-bearing regions and is encoded according to a Hadamard matrix of dimension N by N, where N is a relatively small number. The detected signals are decoded by reference to the same Hadamard matrix. Alternatively a phase-encoding scheme can be employed. Two-dimensional correlation experiments (COSY and TOCSY) and cross-relaxation measurements (NOESY) implemented on proton systems can be completed in less than a minute in cases where the intrinsic sensitivity is sufficiently high that prolonged multiscan averaging is not required. The results are presented in the form of a high-resolution contour diagram similar to the familiar two-dimensional spectra obtained by Fourier transform methods. Experiments on strychnine demonstrate more than two orders of magnitude improvement in speed compared with the traditional methods.     

Hybrid Integration of 1 × 12 Metal-Semiconductor-Metal Photodetector and Polyimide Waveguide Array

We report here a demonstration of hybrid integration of a 1 × 12 metal-semiconductor-metal (MSM) photodetector array and polyimide channel waveguides via 45° total-internal-reflection (TIR) micro-couplers. The two-layer polyimide waveguide array was constructed using Ultradel 9120D for the core and Ultradel 9020 for the lower cladding layer. The coupling loss and propagation loss of the waveguide are 0.2dB and 0.21 dB/cm, respectively. The cross talk of the adjacent channels is -32 dB. The MSM photodetector array was fabricated on a semi-insulated GaAs wafer. The photodetectors are integrated to operate in the conventional vertical illumination mode. We measured the external quantum-efficiency and 3 dB bandwidth of the integrated MSM photodetectors at 0.4 A/W and 2.648 GHz, respectively. The aggregate 3 dB bandwidth of the 12-channel integrated system is 32 GHz.     

A lipophilic hexaporphyrin assembly supported on a stannoxane core

Lipophilic hexaporphyrin free-base and copper-metalated assemblies supported on a Sn6O6 core have been synthesized and characterized. The nuclease activity of the copper derivative has been studied.     

The electronic structure of the isoelectronic, square-planar complexes [FeII(L)2]2- and [CoIII(L Bu)2]- (L2- and (L Bu)2-=benzene-1,2-dithiolates): an experimental and density functional theoretical study

The electronic structures of two formally isoelectronic transition-metal dithiolato complexes [Fe(L)2]2- (1) and [Co(L Bu)2]1- (2) both possessing a spin triplet ground state (St=1) have been investigated by various spectroscopic and density functional methods; H2L Bu represents the pro-ligand 3,5-di-tert-butylbenzene-1,2-dithiol and H2L is the corresponding unsubstituted benzene-1,2-dithiol. An axial zero-field splitting (D) of +32 cm(-1) for 2 has been measured independently by SQUID magnetometry, far-infrared absorption, and variable-temperature and variable-field (VTVH) magnetic circular dichroism spectroscopies. A similar D value of +28 cm(-1) is obtained for 1 on the basis of VTVH SQUID measurements. The absorption spectra of 1 and 2 are found, however, to be very different. Complex 1 is light yellow in color with no intense transition in the visible region, whereas 2 is deep blue. DFT calculations establish that the electronic structures of the [Fe(L)2](2-) and [Co(L)2]1- anions are very different and explain the observed differences in their absorption spectra. On the basis of these spectroscopic and theoretical analyses, 1 is best described as containing an intermediate spin FeII ion, whereas for the corresponding cobalt complex, oxidation states describing a d6 (CoIII) or d7 (CoII) electron configuration cannot be unambiguously assigned. The physical origin of the large zero-field splitting in both 1 and 2 is found to be due to the presence of low-energy spin-conserved d-d excitations which lead to a large Dzz through efficient spin-orbit coupling. Differential covalency effects appear to be of limited importance for this property.     

Conformational Study of Spectrin in Presence of Submolar Concentrations of Denaturants

The presence of very low concentrations of the commonly used chemical denaturants, guanidinium chloride (GdmCl) and urea brought about conformational changes in the erythrocyte membrane skeletal protein, spectrin. Evidences in support of changes in the quaternary structure of spectrin have been put forward from quenching study of tryptophan fluorescence, by both steady state and time-resolved measurements, using acrylamide as the quencher. It revealed significant differences between the Stern–Volmer quenching constants (K_SV) and the fraction of accessible tryptophans (f_e) observed in absence and presence of GdmCl and urea concentrations below 1 M at which the association of the two subunits remains intact. The steady state anisotropy of both the spectrin tryptophans and the spectrin-bound fluorescence probe, Prodan also indicate changes in the overall flexibility of the spectrin dimer, originating from changes in the quaternary structure of spectrin. Studies on the binding of Prodan, further indicate that conformational changes also occur in spectrin near the Prodan-binding site at the terminal domain of the protein which is reflected in 3–4 fold decrease in the affinity of binding of Prodan to spectrin in the presence of GdmCl and urea compared to that observed in the absence of the denaturants. The dissociation constant (K_d) of Prodan to spectrin is 0.43 M at 25°C.