Reducing Huge Gyroscopic Eigenproblems by Automated Multi-level Substructuring

Simulating numerically the sound radiation of a rolling tire requires the solution of a very large and sparse gyroscopic eigenvalue problem. Taking advantage of the automated multi-level substructuring (AMLS) method it can be projected to a much smaller gyroscopic problem, the solution of which however is still quite costly since the eigenmodes are non-real and complex arithmetic is necessary. This paper discusses the application of AMLS to huge gyroscopic problems and the numerical solution of the AMLS reduction. A numerical example demonstrates the efficiency of AMLS.     

Strongly confined quantum wire states in strained T-shaped GaAs/InAlAs structures

The confinement energy of T-shaped quantum wires (QWRs), which were fabricated by the cleaved edge overgrowth technique in a way that the QWRs form at the intersection of In_0.2Al_0.8As stressor layers and the overgrown (1 1 0) GaAs quantum well (QW), is examined using micro-photoluminescence spectroscopy. Photoluminescence (PL) signals from individual QWRs can be spatially resolved, since the strained films are separated by 1 μm wide Al_0.3Ga_0.7As layers. We find that due to the tensile strain being transmitted to the QW, the confinement energy of the QWRs rises systematically up to 40 meV with increasing thickness of the stressor layers. By reducing the excitation power to 0.1 μW the QWR PL emission occurs 48 meV redshifted with respect to the QW. All QWR peaks exhibit smooth lineshapes, indicating the absence of pronounced exciton localization.     

DEMONSTRATION THAT PHOSPHORESCENT 6-BROMO-2-NAPHTHYL SULFATE CAN BE USED TO PROBE HEME ACCESSIBILITY IN HEME PROTEINS

The phosphorescence properties of 6-bromo-2-naphthyl sulfate (BNS) in aqueous solution were studied. The phosphorescence lifetime is several hundred microseconds and is self-quenched. Although a fluorescent photoproduct is formed from BNS, it does not interfere with the decay properties of triplet-state BNS and its utility as a probe of the accessibility of the heme group in heme proteins. Quenching of BNS phosphorescence does not occur for the non-heme protein lysozyme and apomyoglobin but occurs by a dynamic mechanism with a quenching constant of 1-2 x 10(9) M-1 s-1 for cytochrome c and myoglobin and with a quenching constant of 6.2 x 10(9) M-1 s-1 for protoporphyrin IX. The phosphorescence of an inclusion complex of 1-bromonaphthalene and beta-cyclodextrin is not quenched by heme-containing proteins. The temperature and viscosity dependencies of the rate with which BNS phosphorescence is quenched by microperoxidase-11 are consistent with unit quenching efficiency. These results indicate that quenching of BNS phosphorescence occurs only upon contact with the quencher, and the quenching constant can be used to assess the degree of accessibility of the heme group.     

Heterocyclic Spiro-naphthalenones. Part III. Synthesis and reactions of some spiro [naphthalene-1,2′-pyrrolidin]-2-ones and spiro [naphthalene-2,2′-pyrrolidin]-1-ones

The spironaphthalen-2-ones 2, 10 and 18 were prepared by N-bromosuccinimide (NBS) oxidation of 1, 9 and 17 respectively, whereas spironaphthalen-1-ones 24 and 25 were obtained by treating 23 with NBS. The stereoisomeric reduction products 29, 30 and 32 obtained from 24 and 25 , gave the pentacyclic compound 33 on treatment with polyphosphoric acid.     

Stark- and Zeeman-effect of resonance lines of Ba I

Laserspectroscopic investigations were performed on a collimated atomic beam of barium (natural isotope abundance). The metastable ground levels (³D_1,2,3 and ¹D₂) of the investigated lines were populated by a discharge burning in barium vapour directly in front of the oven hole. We could investigate 14 spectral lines between 580 and 690 nm. The tensor polarizabilities of the upper and the lower level as well as the differences in the scalar polarizabilities could be determined. Spectra in magnetic fields up to 0.03 Tesla showed no deviation from the pattern resulting from a simple Russell-Sounders coupling.     

Metal "capture" by a heterotrimetalloligand, heterometallic d(10)-d(10) interactions, and unexpected iron-to-platinum silyl ligand migration: a combined experimental and theoretical study

The heterotrinuclear chain complex Hg[Fe{Si(OMe)(3)}(CO)(3)(dppm-P)](2) (dppm = Ph(2)PCH(2)PPh(2)) 1 which has a transoid arrangement of the phosphine donors was used as a versatile chelating metallodiphosphine ligand owing to the easy rotation of its metal core about the Fe-Hg sigma-bonds. Its reaction with the labile Pt(0) olefin complex [Pt(C(7)H(10))(3)] yielded [HgPt{Si(OMe)(3)}Fe(2)(CO)(6){Si(OMe)(3)}(mu-dppm)(2)] 5 which resulted, after coordination of the dangling phosphine donors to Pt, from an unprecedented intramolecular rearrangement involving a very rare example of silyl ligand migration between two different metal centers, and the first one in metal cluster chemistry. The major structural differences observed between the heterometallic complexes obtained from 1 and d(10) Cu(I), Pd(0), or Pt(0) precursors have been established by X-ray diffraction. The bonding situation in the silyl migrated Pt complex 5 was analyzed and compared to those in the isoelectronic, but structurally distinct complexes obtained from Cu(I) and Pd(0) precursors, [Hg{Fe[Si(OMe)(3)](CO)(3)(mu-dppm)}(2)Cu](+) (2) and [Hg{Fe[Si(OMe)(3)](CO)(3)(mu-dppm)}(2)Pd] (4), respectively, by means of extended Hückel interaction diagrams. DFT calculations then allowed the energy minima associated with the three structures to be compared for 2, 4, and 5. All three minima are in close competition for the Pd complex 4, but silyl migration is favored by approximately 10 kcal mol(-)(1) for 5, mainly due to the more electronegative character of Pt with respect to Pd.     

Renormalization group treatment of phase transitions in ferromagnetic superconductors

We investigate the nature of the phase transition from the superconducting to the uniformly ordered magnetic phase in ferromagnetic superconductors by renormalization group methods. For this purpose Halperin, Lubensky, Ma's application of the-expansion to pure superconductors is extended to include the influence of magnetic order as well. Our treatment shows that in the vicinity of the ferromagnetic to superconducting phase-boundary critical fluctuations of the magnetization are absorbed into fluctuations of the magnetic field. As a consequence the transition always is first order. An additional indication to the dominance of electromagnetic effects is the irrelevance of the coupling corresponding to spin flip scattering.     

Synthesis of Structurally Complex Silicon Frameworks through the First Sila-Aldol Reaction

Herein, we report on the first sila-aldol reaction, which emphasizes the tight connection between silicon and carbon chemistry. This novel synthetic method provides straightforward access to 2-oxahexasilabicyclo[3.2.1]octan-8-ide, a structurally complex silicon framework, in quantitative yield. Its structure was confirmed by NMR spectroscopy and X-ray crystallography, and it displays a distinctive charge-transfer transition. The complete mechanism of this highly selective rearrangement cascade is outlined and supported by density functional theory (DFT) calculations, which highlight the thermodynamic driving force and the low activation barriers of this powerful silicon–carbon bond-forming strategy.     

Lifetimes of triplet state alkylbenzenes in the vapor phase

Rate constants for triplet state decay of C₆H₆, C₆D₆ and 15 alkylbenzenes in the vapor phase have been found, using a flash-sensitized biacetyl phosphorescence technique, to range between 800 s^?1 and ? 18 000 s^?1. Only benzene has a significant positive activation energy for decay. Kinetic and spectroscopic evidence supports a photoisomerization decay channel in t-butylbenzene. Comparison of lifetimes with molecular size shows that increased density of rotational levels does not account for rapid decay of the triplet state. This contradicts a recent suggestion to explain short lifetimes of triplet state aromatic hydrocarbons in the vapor phase, relative to the long lifetimes of the same molecules in low temperat matrices. Evidence suggests that the dominant decay paths for triplet state alkylbenzenes are different in room temperature vapors and low temperature matrices.