Roofed polyquinanes: synthesis and electronic structure

Starting from readily available norbornenobenzoquinone 7 and employing a photothermal metathesis reaction as the main strategy, novel "roofed" polyquinane bisenones 3 and 13 have been synthesized. Among these, the former is potentially serviceable for further elaboration to dodecahedrane 1. Catalytic hydrogenation of 3 provided the dione 12, which fully inscribes the circumference of dodecahedrane sphere. The "roofed" C-16-bisenone 3 has been successfully annulated to C19-bisenone 24 and C19-trisenone 26 by employing the Greene methodology and Pauson-Khand reaction, respectively. The molecular structures of 3 and 13 were computed using molecular mechanics and semiempirical MO methods. The nonbonded distances between the double bonds vary strongly with the method employed. The interactions between the pi-MO's were, therefore, probed by means of photoelectron (PE) spectroscopy. Comparison with the PE spectra of a series of model systems with increasing complexity enabled an unambiguous assignment of the observed peaks. The symmetric and antisymmetric combinations of the pi-MO's of the enone moieties of 3 and 13 show large splittings, characteristic of propano-bridged systems in which through-space and through-bond effects act in concert.

A measurement technique for low frequencies

A technique for the measurement of frequency within a cycle of a periodic input is described. This can be useful for quicker measurement of low frequencies.

Amplitude Frequency Response Measurement: A Simple Technique

A simple method is described to combine a modern function generator and a digital oscilloscope to configure a setup that can directly measure the amplitude frequency response of a system. This is achieved by synchronously triggering both instruments, with the function generator operated in the ``Linear-Sweep'' frequency mode, while the oscilloscope is operated in the ``Envelope'' acquisition mode. Under these conditions, the acquired envelopes directly correspond to the (input and output signal) spectra, whose ratio yields the amplitude frequency response. The method is easy to configure, automatic, time-efficient, and does not require any external control or interface or programming. This method is ideally suited to impart hands-on experience in sweep frequency response measurements, demonstrate resonance phenomenon in transformer windings, explain the working principle of an impedance analyzer, practically exhibit properties of network functions, and so on. The proposed method is an inexpensive alternative to existing commercial equipment meant for this job and is also an effective teaching aid. Details of its implementation, along with some practical measurements on an actual transformer, are presented.

Analysis of conjugate laminar mixed convection cooling in a shrouded array of electronic components

The temperature variation in the insulation around an electronic component, mounted on a horizontal circuit board is studied numerically. The flow is assumed to be laminar and fully developed. The effect of mixed convection and two different types of insulation are considered. The mass, momentum and energy conservation equations in the fluid and conduction equation in the insulation are solved using the SIMPLER algorithm. Computations are carried out for liquid Freon and water, for different conductivity ratios, and different Rayleigh numbers. It is demonstrated that the temperature variation within the insulation becomes important when the thermal conductivity of the insulation is less than ten times the thermal conductivity of the cooling medium.

On measurement of top polarization as a probe of t(t)over-bar production mechanisms at the LHC

In this note we demonstrate the use of top polarization in the study of t (t) over bar resonances at the LHC, in the possible case where the dynamics implies a non-zero top polarization. As a probe of top polarization we construct an asymmetry in the decay-lepton azimuthal angle distribution (corresponding to the sign of cos phi(l)) in the laboratory. The asymmetry is non-vanishing even for a symmetric collider like the LHC, where a positive z axis is not uniquely defined. The angular distribution of the leptons has the advantage of being a faithful top-spin analyzer, unaffected by possible anomalous tbW couplings, to linear order. We study, for purposes of demonstration, the case of a Z' as might exist in the little Higgs models. We identify kinematic cuts which ensure that our asymmetry reflects the polarization in sign and magnitude. We investigate possibilities at the LHC with two energy options: root s = 14TeV and root s = 7TeV, as well as at the Tevatron. At the LHC the model predicts net top quark polarization of the order of a few per cent for M-Z' similar or equal to 1200GeV, being as high as 10% for a smaller mass of the Z' of 700GeV and for the largest allowed coupling in the model, the values being higher for the 7TeV option. These polarizations translate to a deviation from the standard-model value of azimuthal asymmetry of up to about 4% (7%) for 14 (7) TeV LHC, whereas for the Tevatron, values as high as 12% are attained. For the 14TeV LHC with an integrated luminosity of 10 fb(-1), these numbers translate into a 3 sigma sensitivity over a large part of the range 500 less than or similar to M-Z' less than or similar to 1500GeV.

Electronic states in a disordered metal: Magnetotransport in doped germanium

We observe a sharp feature in the ultra-low-temperature magnetoconductivity of degenerately doped Ge:Sb at H∼25 kOe, which is robust up to at least three times the critical density for the insulator-metal transition. This field corresponds to a low-energy scale characteristic of the special nature of antimony donors in germanium. Its presence and sensitivity to uniaxial stress confirm the notion of metallic impurity bands in doped germanium.

Conformation of substituted polyacetylenes in solution : relationship between electronic properties and local order

A study of the chain conformation in solutions of polyphenylacetylene and poly(2-octyne) has been performed. The two polymers differ in many ways : polyphenylacetylene gives a red solution while poly(2-octyne) is transparent and, a marked difference on the chain rigidity is observed : the statistical length are 45 Å and 135 Å respectively. From the study of these two systems, one deduces that curvature fluctuations play a minor role on the π electrons localization, and that the torsion between monomer units is the pertinent parameter to understand the chain conformation and the π electrons localization.

Electronic Structure of and the Metal-Insulator Transition in La1-xSrxCoO3-δ: A Soft-X-Ray Absorption Study

We report the soft-X-ray absorption spectra at the oxygen K-edge of La1-xSrxCoO3-δ (x = 0.0, 0.1, 0.2, 0.3 and 0.4) series with experimentally determined δ values. We show that the doping of holes by replacing La3+ with Sr2+ induces states within the band gap of the insulating undoped compound for small x and these doped states have a very substantial oxygen 2p character. This indicates that the insulating compounds belong to the charge transfer insulator regime. With increasing Sr content, the doped states broaden into a band overlapping the top of the primarily oxygen p-derived band, leading to an insulator-metal transition at x ≥ 0.2.

Electronic absorption and emission spectroscopic investigations of the interaction of the fullerenes, C60 and C70, with amines and aromatic molecules

Electronic absorption spectroscopy and fluorescence spectroscopy have been used to investigate the interaction of the fullerenes C60 and C70 with diethylaniline, and with aromatic solvents such as benzene. C60 interacts weakly with aromatic amines in the ground state while C70 does not interact at all. Steady state fluorescence emission and lifetime measurements show that both C60 and C70 form excited state complexes (exciplexes) with the amines in non-aromatic solvents such as methylcyclohexane, but not in benzene. In benzene, only fluorescence quenching is observed due to the interaction between the π systems of the aromatic solvent and the fullerene in the ground state. This is also borne out by the systematic study of solvent effects on the absorption and emission spectra of the fullerenes.

Electronic excitations and alternation of conjugated polymers

The electronic excitations and fluorescence of conjugated polymers are related to large or small alternation ? of the transfer integrals t(1 ± ?) along the backbone. The fluorescence of polysilanes (PSs) and poly (para-phenylenevinylene (PPV) is linked to large ?, which places the one-photon gap Eg below the lowest two-photon gap Ea and reduces distortions due to electron-phonon (e-p) coupling. In contrast to small ? not, vert, similar 0.1 in ?-conjugated polymers, such as polyacetylene (PA), para-conjugated phenyls lead to an extended ?-system with increased alternation, to states localized on each ring and to charge-transfer excitations between them. Surprisingly good agreement is found between semiempirical parametric method 3 (PM3) bond lengths and exact Pariser-Parr-Pople (PPP) ?-bond orders for trans-stilbene, where the PPV bipolarons are confined to two phenyls. Stilbene spectra are consistent with increased alternation and small e-p distortions.

Electronic structure of La1-xSrxFeO3

We have investigated the electronic structure of well-characterized samples of La1-xSrxFeO3 (x=0.0�0.4) by x-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy, bremsstrahlung isochromat (BI) spectroscopy, and Auger electron spectroscopy. We find systematic behavior in the occupied and unoccupied density of states reflecting changes in the electronic structure on hole doping via Sr substitution as well as providing estimates for different interaction strengths. The spectral features, particularly of the unoccupied states obtained from BI spectra, indicate the probable reason for the absence of an insulator-metal transition in this series. Analysis of the Auger spectra provides the estimates of the on-site effective Coulomb interaction strengths in Fe 3d and O 2p states. The parameter values for the bare charge-transfer energy ? and the Fe 3d�O 2p hybridization strength t? for LaFeO3 are obtained from an analysis of the Fe 2p core-level XPS in terms of a model many-body calculation. We discuss the character of the ground state in LaFeO3 as well as the nature of the doped hole states in La1-xSrxFeO3, based on these parameter values.