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51.
Wolf R Ehlers AW Khusniyarov MM Hartl F de Bruin B Long GJ Grandjean F Schappacher FM Pöttgen R Slootweg JC Lutz M Spek AL Lammertsma K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(48):14322-14334
The preparation and comprehensive characterization of a series of homoleptic sandwich complexes containing diphosphacyclobutadiene ligands are reported. Compounds [K([18]crown-6)(thf)(2)][Fe(η(4)-P(2)C(2)tBu(2))(2)] (K1), [K([18]crown-6)(thf)(2)][Co(η(4)-P(2)C(2)tBu(2))(2)] (K2), and [K([18]crown-6)(thf)(2)][Co(η(4)-P(2)C(2)Ad(2))(2)] (K3, Ad = adamantyl) were obtained from reactions of [K([18]crown-6)(thf)(2)][M(η(4)-C(14)H(10))(2)] (M = Fe, Co) with tBuC[triple bond]P (1, 2), or with AdC[triple bond]P (3). Neutral sandwiches [M(η(4)-P(2)C(2)tBu(2))(2)] (4: M = Fe 5: M = Co) were obtained by oxidizing 1 and 2 with [Cp(2)Fe]PF(6). Cyclic voltammetry and spectro-electrochemistry indicate that the two [M(η(4)-P(2)C(2)tBu(2))(2)](-)/[M(η(4)-P(2)C(2)tBu(2))(2)] moieties can be reversibly interconverted by one electron oxidation and reduction, respectively. Complexes 1-5 were characterized by multinuclear NMR, EPR (1 and 5), UV/Vis, and M?ssbauer spectroscopies (1 and 4), mass spectrometry (4 and 5), and microanalysis (1-3). The molecular structures of 1-5 were determined by using X-ray crystallography. Essentially D(2d)-symmetric structures were found for all five complexes, which show the two 1,3-diphosphacyclobutadiene rings in a staggered orientation. Density functional theory calculations revealed the importance of covalent metal-ligand π bonding in 1-5. Possible oxidation state assignments for the metal ions are discussed. 相似文献
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53.
A two‐dimensional simulation of a plane jet exhausting from a channel has been performed using the vortex in cell algorithm in the Reynolds number range of 100–900. The vorticity is generated on the wall of the entrance channel whose length has been fixed in order to obtain a fully developed velocity profile at the entry of the jet. The transient behaviour of the velocity field starting from rest has been observed until reaching a quasi steady regime. The mean value of the velocity field is compared with the results of a finite volume computation on the same mesh. The velocity fluctuations obtained using this method are analysed. Their effect on the mean flow is estimated to be smaller than the viscous effect. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
54.
The performance of parallel subdomain method with overlapping is analysed in the case of the 3D coupled boundary‐value problem of continuous flow electrophoresis which is governed by Navier–Stokes equations coupled with convection–diffusion and potential equations. Convergence of parallel synchronous and asynchronous iterative algorithms is studied. Comparison between implemented explicit and implicit schemes for the transport equation is made using these algorithms and shows that both methods provide similar results and comparable performances. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
55.
Hazra S Sasmal S Fleck M Grandjean F Sougrati MT Ghosh M Harris TD Bonville P Long GJ Mohanta S 《The Journal of chemical physics》2011,134(17):174507
The magnetic, electronic, and Mo?ssbauer spectral properties of [Fe(2)L(μ-OAc)(2)]ClO(4), 1, where L is the dianion of the tetraimino-diphenolate macrocyclic ligand, H(2)L, indicate that 1 is a class III mixed valence iron(II∕III) complex with an electron that is fully delocalized between two crystallographically inequivalent iron sites to yield a [Fe(2)](V) cationic configuration with a S(t) = 9∕2 ground state. Fits of the dc magnetic susceptibility between 2 and 300 K and of the isofield variable-temperature magnetization of 1 yield an isotropic magnetic exchange parameter, J, of -32(2) cm(-1) for an electron transfer parameter, B, of 950 cm(-1), a zero-field uniaxial D(9∕2) parameter of -0.9(1) cm(-1), and g = 1.95(5). In agreement with the presence of uniaxial magnetic anisotropy, ac susceptibility measurements reveal that 1 is a single-molecule magnet at low temperature with a single molecule magnetic effective relaxation barrier, U(eff), of 9.8 cm(-1). At 5.25 K the Mo?ssbauer spectra of 1 exhibit two spectral components, assigned to the two crystallographically inequivalent iron sites with a static effective hyperfine field; as the temperature increases from 7 to 310 K, the spectra exhibit increasingly rapid relaxation of the hyperfine field on the iron-57 Larmor precession time of 5 × 10(-8) s. A fit of the temperature dependence of the average effective hyperfine field yields |D(9∕2)| = 0.9 cm(-1). An Arrhenius plot of the logarithm of the relaxation frequency between 5 and 85 K yields a relaxation barrier of 17 cm(-1). 相似文献
56.
Abramowski A Acero F Aharonian F Akhperjanian AG Anton G Barnacka A de Almeida UB Bazer-Bachi AR Becherini Y Becker J Behera B Bernlöhr K Bochow A Boisson C Bolmont J Bordas P Borrel V Brucker J Brun F Brun P Bulik T Büsching I Carrigan S Casanova S Cerruti M Chadwick PM Charbonnier A Chaves RC Cheesebrough A Chounet LM Clapson AC Coignet G Conrad J Dalton M Daniel MK Davids ID Degrange B Deil C Dickinson HJ Djannati-Ataï A Domainko W Drury LO Dubois F Dubus G Dyks J Dyrda M Egberts K Eger P 《Physical review letters》2011,106(16):161301
A search for a very-high-energy (VHE; ≥100 GeV) γ-ray signal from self-annihilating particle dark matter (DM) is performed towards a region of projected distance r~45-150 pc from the Galactic center. The background-subtracted γ-ray spectrum measured with the High Energy Stereoscopic System (H.E.S.S.) γ-ray instrument in the energy range between 300 GeV and 30 TeV shows no hint of a residual γ-ray flux. Assuming conventional Navarro-Frenk-White and Einasto density profiles, limits are derived on the velocity-weighted annihilation cross section (σv) as a function of the DM particle mass. These are among the best reported so far for this energy range and in particular differ only little between the chosen density profile parametrizations. In particular, for the DM particle mass of ~1 TeV, values for (σv) above 3×10(-25) cm(3)?s(-1) are excluded for the Einasto density profile. 相似文献
57.
58.
Sylvain Petit Stéphane Pailhès Xavier Fabrèges Martine Hennion Fernande Moussa Loreynne Pinsard Louis-Pierre Regnault Alexander Ivanov 《Pramana》2008,71(4):869-876
Aiming to shed light on the possible existence of hybrid phonon-magnon excitations in multiferroic manganites, neutron scattering
measurements have been undertaken at LLB and ILL on the particular case of hexagonal YMnO3. Our experiments focused on a transverse acoustic phonon mode polarized along the ferroelectric axis. The neutron data show
that below the magnetic transition, this particular phonon mode splits in two different branches. The upper branch is found
to coincide with a spin wave mode. This manifestation of a strong spin-lattice coupling is discussed in terms of a possible
hybridization between the two types of elementary excitations, the phonon and magnons.
相似文献
59.
Fernande Grandjean Gary J. Long Christopher G. Benson Umberto Russo 《Hyperfine Interactions》1988,40(1-4):299-302
The Mössbauer effect spectra of Fe3(CO)12 have been measured from 4.2 to 295 K and reveal an unusual temperature dependence in the relative area of the two components of the quadrupole doublet associated with the two equivalent iron sites and in the relative area of the two observed quadrupole doublets. The asymmetry in the outer quadrupole doublet is attributed to the Goldanskii-Karyagin effect. The strong temperature dependence of the relative areas of the two quadrupole doublets results from a differing temperature dependence of the recoil free fractions for the two chemically different sites. 相似文献
60.
Gary J. Long Dimitri Hautot Fernande Grandjean D. Vandormael H. P. Leighly Jr. 《Hyperfine Interactions》2004,155(1-4):1-13
The recent recovery of steel from the Titanic has permitted a 295 K conversion electron Mössbauer spectral study of the Titanic hull plate steel oriented with the gamma-ray direction either perpendicular or parallel to the microstructural banding directions. The two spectra reveal virtually identical average orientations of the magnetization close to the plane of the plate. The hyperfine parameters are virtually identical to those of α-iron, a finding which agrees with the chemical analysis which reveals at most 0.21 wt% carbon corresponding to 3 wt% of cementite in pearlite. A 4.2 to 295 K transmission Mössbauer spectral study of the rusticles reveals small particles of geothite undergoing superparamagnetic relaxation with a blocking temperature of ca. 300 K. In addition approximately two percent of the Mössbauer spectral absorption area corresponds to a quadrupole doublet with hyperfine parameters typical of green rust. The identified iron containing components in the rusticles agree with the powder X-ray diffraction results which reveal the predominant presence of small particles of poorly crystallized goethite and traces of quartz and green rust. An average size of 20±5 nm for the goethite particles is obtained from both the average hyperfine field and the broadening of the X-ray diffraction peaks. The magnetic anisotropy constant of the goethite particles deduced from the hyperfine field and the particle size is 8×103 J/m3. 相似文献