Crystal Structure and Magnetic Properties of SrCaMnGaO5+δ

The room-temperature crystal structure of the brownmillerite SrCaMnGaO_5+δ (δ=0.035) has been refined from neutron powder diffraction data; space group Ima2, a=15.7817(6), b=5.4925(2), c=5.3196(2)> Å. Mn and Ga occupy 99.0(2)% of the 6- and 4-coordinate sites, respectively. A combination of magnetometry, neutron diffraction and μSR spectroscopy has shown that the compound orders magnetically at 180 K, and that the low-temperature phase has a G-type antiferromagnetic structure, with an ordered magnetic moment of 3.30(2) μ_B per Mn at 2 K. Displaced hysteresis loops provide evidence that the atomic moment has an additional, glassy component. Magnetometry shows that significant short-range magnetic interactions persist above 180 K, and μSR that the spin fluctuations are thermally activated in this temperature region. The compound is an electrical insulator which at 159 K shows an unusually large magnetoresistance of 85% in 6 T, increasing to 90% in 13 T.     

Overtone spectroscopy of some benzaldehyde derivatives

Overtone spectrum of o, m and p-nitrobenzaldehydes and p-chlorobenzaldehyde has been studied in 2000–12000 cm⁻¹ region. Vibrational frequencies and anharmonicity constants for aryl as well as alkyl CH stretch vibrations have been determined. We have also determined the internuclear distances for the aryl CH bond in the different molecules. The small variation observed in these distances is an indication of the substitution effect. It is observed that in the case of p-disubstituted benzens, the shift in aryl CH bond is proportional to sum of the Hammet σ of the substituents. However in the case of o-disubstituted benzenes it is only 80% of the para-substituted shift.     

Solid state broadening in Auger spectra

Some Auger spectra in the gas phase show extremely sharp lines and a great deal of fine structure while the Auger spectra of solids, even at high resolution, lack this detailed fine structure and generally have much broader peaks. In an effort to understand the broadening processes which occur on condensation of a gas or vapour to the solid phase, several solids for which high resolution gas phase data exists have been studied. The result of measurements of the M₄₅N₄₅N₄₅ Auger spectrum of cadmium are reported and comparison is made with the vapour phase data. Although the solid data contains considerable quasi-atomic fine structure the lines are broader than the vapour phase and by matching computer broadened vapour phase data to the experimental data an estimate of the individual line widths may be made. The relative intensities of the lines in the simulation agree closely with the solid data if loss processes are considered. Measurements have also been made on the same Cd transition in CdS and in this material the Auger lines are much broader than in Cd metal and the fine structure has almost disappeared. Results are also reported of measurements of the Auger spectra of solid rare gases made with the aid of a UHV cryostat capable of operating at temperatures down to 10 K. The gases studied were Xe, Ar and Kr and again comparison with computer broadened gas data enable the broadening of individual Auger lines to be estimated. Measurements of the line breadths have been made at various temperatures and the results of these experiments will be discussed in terms of lifetime and lattice vibrational broadening.     

Solid state broadening effects in the Auger spectrum of xenon

The M_4,5N_4,5 Auger spectrum has been measured at high resolution from solid xenon. Comparison with the gas phase data shows that considerable broadening of the Auger lines occurs in the solid. Electron energy loss data is also reported for solid xenon.     

Development of a method for the preparation of ruthenium indenylidene-ether olefin metathesis catalysts

The reactions between several derivatives of 1-(3,5-dimethoxyphenyl)-prop-2-yn-1-ol and different ruthenium starting materials [i.e., RuCl?(PPh?)? and RuCl?(p-cymene)(L), where L is tricyclohexylphosphine di-t-butylmethylphosphine, dicyclohexylphenylphosphine, triisobutylphosphine, triisopropylphosphine, or tri-n-propylphosphine] are described. Several of these reactions allow for the easy, in-situ and atom-economic preparation of olefin metathesis catalysts. Organic precursor 1-(3,5-dimethoxyphenyl)-1-phenyl-prop-2-yn-1-ol led to the formation of active ruthenium indenylidene-ether complexes, while 1-(3,5-dimethoxyphenyl)-prop-2-yn-1-ol and 1-(3,5-dimethoxyphenyl)-1-methyl-prop-2-yn-1-ol did not. It was also found that a bulky and strong σ-donor phosphine ligand was required to impart good catalytic activity to the new ruthenium complexes.     

Extremes of nuclear structure

With the advent of medium and large gamma detector arrays, it is now possible to look at nuclear structure at high rotational forces. The role of pairing correlations and their eventual breakdown, along with the shell effects have showed us the interesting physics for nuclei at high spins — superdeformation, shape co-existence, yrast traps, alignments and their dramatic effects on nuclear structure and so on. Nuclear structure studies have recently become even more exciting, due to efforts and possibilities to reach nuclei far off from the stability valley. Coupling of gamma ray arrays with ‘filters’, like neutron wall, charged particle detector array, gamma ray total energy and multiplicity castles, conversion electron spectrometers etc gives a great handle to study nuclei produced online with ‘low’ cross-sections. Recently we studied, nuclei in mass region 80 using an array of 8 germanium detectors in conjunction with the recoil mass analyser, HIRA at the Nuclear Science Centre and, most unexpectedly came across the phenomenon of identical bands, with two quasi-particle difference. The discovery of magnetic rotation is another highlight. Our study of light In nucleus, 107In brought us face to face with the ‘dipole’ bands. I plan to discuss some of these aspects. There is also an immensely important development — that of the ‘radioactive ion beams’. The availability of RIB, will probably very dramatically influence our ‘conventional’ concept of nuclear structure. The exotic shapes of these exotic nuclei and some of their expected properties will also be touched upon.     

Auger emission and colour centres in lithium fluoride

Low energy Auger transitions from lithium fluoride, below 50 eV, have been associated by Gallon and Matthew [Phys. Status Solidi 41 (1970) 343] with transition processes between an ionised lithium ion and neighbouring fluorine ions. Two of these transitions, giving rise to lines at 36 eV and 43 eV were thought to involve de-excitation via colour centre defects. The growth behaviour of these lines has been investigated as a function of temperature, between 200°K and 600°K, and correlations have been established between this behaviour and optical absorption data obtained in situ. The effects of deposited nickel films on the Auger spectrum have also been investigated, and it is concluded that the 43 eV transition arises from lithium metal produced by electron beam dissociation of the lithium fluoride while the 36 eV line does indeed arise from de-excitation via a defect centre.     

Preparation, structural analysis and dielectric properties of Bi x La1−x FeO3 perovskite

Rare earth element substituted bismuth ferrites (BiFeO₃) are of enormous importance as magnetoelectric materials. The polycrystalline samples of Bi _x La_1−x FeO₃ (x=0, 0.2, 0.4, 0.6, 0.8) were prepared by solid-state reaction using standard ceramic method. The single-phase formation of these compounds was confirmed by X-ray diffraction (XRD) studies. The samples with x=0, 0.2, 0.4, 0.6 are found to be orthorhombic while the sample with x=0.8 is triclinic. The dielectric constant (ε′) and dissipation factor (tan δ) were measured in the frequency range 100 Hz to 1 MHz at room temperature and as a function of temperature at certain fixed frequencies (1 kHz, 10 kHz, 100 kHz, 1 MHz). All the samples showed dielectric dispersion. The dielectric constant with temperature shows a broad peak; the peak temperature shifts with frequency which reflects the relaxor-type behavior. The peak above 600 K in the measured temperature range corresponds to antiferromagnetic ordering temperature (Néel temperature). The broadness of the peak changes with composition. The ac conductivity as well as ε′ are found to be maximum for the sample x=0.2 at room temperature.