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81.
82.
Bradley A. Ochs Dan Fries Devesh Ranjan Suresh Menon 《Flow, Turbulence and Combustion》2018,101(3):927-951
It is unclear whether turbulent flame speed scalings established in low speed regimes are applicable to supersonic flames. To investigate this question, the canonical flame kernel is investigated in a scramjet-like channel having a one degree wall divergence. The growth, shape and internal kernel dynamics are investigated. Results are presented for three Mach numbers, four equivalence ratios, and three turbulence generators. Schlieren photography provides flame images for growth rate statistics and particle image velocimetry (PIV) provides turbulence statistics and investigation of internal kernel dynamics. Supersonic flame kernels are self-propagating and respond to the equivalence ratio in a fashion that is similar to low speed flames. However, supersonic flame kernels have features that are not present in subsonic flame kernels. Baroclinicity, resulting from pressure-density misalignment, creates a reacting vortex ring structure. Further, the mean kernel shape has a Mach number dependence and the vortex ring enhances the turbulent flame speed through entrainment of reactants and augmented flame surface growth. Hence, the previously established (low speed) flame speed scalings are inappropriate for supersonic flame kernels. Drawing motivation from vortex ring literature, the ring propagation velocity is used as the characteristic velocity and a new flame speed scaling is proposed. 相似文献
83.
84.
Depending on the synthetic conditions, five heterometallic Mn(III)Fe(II) polynuclear compounds with the same ratio of constituents, 2[Mn(acacen)](+)/[Fe(CN)(5)NO](2-), of different nuclearity and dimensionality (0D, 1D, 2D) were isolated. A [Mn(acacen)MeOH](2)[Fe(CN)(5)NO]·1.5MeOH, 1 complex has been prepared by reaction of Mn(III)/Schiff base (SB) complex, [Mn(acacen)Cl] (H(2)acacen is N,N'-ethylenebis(acetylacetoneimine)) with sodium nitroprusside (NP). Single crystal X-ray diffraction analyses reveal that crystallization of 1 from coordinating or non-coordinating solvents results in different coordination polynuclear materials: from C(2)H(5)OH [{Mn(acacen)H(2)O}(2)Fe(CN)(5)NO]·C(2)H(5)OH, 2, a trinuclear complex is formed; from CH(3)CN [{Mn(acacen)H(2)O}(4)Fe(CN)(5)NO][Fe(CN)(5)NO]·4CH(3)CN, an ionic compound with a pentanuclear bimetallic cation is formed 3; from i-C(3)H(7)OH [{Mn(acacen)}(2)(i-PrOH)Fe(CN)(5)NO](n), a coordination chain polymer 4 is formed; from toluene [{Mn(acacen)}(2)Fe(CN)(5)NO](n), a layered network 5 is formed. As the magnetic measurements show, for all compounds the weak interaction between Mn(III)S = 2 spins through the NP bridge is antiferromagnetic and exhibits no significant photoactivity. 相似文献
85.
Kira M 《Proceedings of the Japan Academy. Series B, Physical and biological sciences》2012,88(5):167-191
Structure and properties of silicon-silicon doubly bonded compounds (disilenes) are shown to be remarkably different from those of alkenes. X-Ray structural analysis of a series of acyclic tetrakis(trialkylsilyl)disilenes has shown that the geometry of these disilenes is quite flexible, and planar, twist or trans-bent depending on the bulkiness and shape of the trialkylsilyl substituents. Thermal and photochemical interconversion between a cyclotetrasilene and the corresponding bicyclo[1.1.0]tetrasilane occurs via either 1,2-silyl migration or a concerted electrocyclic reaction depending on the ring substituents without intermediacy of the corresponding tetrasila-1,3-diene. Theoretical and spectroscopic studies of a stable spiropentasiladiene have revealed a unique feature of the spiroconjugation in this system. Starting with a stable dialkylsilylene, a number of elaborated disilenes including trisilaallene and its germanium congeners are synthesized. Unlike carbon allenes, the trisilaallene has remarkably bent and fluxional geometry, suggesting the importance of the π-σ* orbital mixing. 14-Electron three-coordinate disilene-palladium complexes are found to have much stronger π-complex character than related 16-electron tetracoordinate complexes. 相似文献
86.
In a reference frame rigidly bound to the complex, we consider two Hamiltonians possibly at the origin of the very fast electronic relaxation of the paramagnetic lanthanide Ln(3+) ions (Ln = Ce to Nd, Tb to Yb), namely the mean (static) ligand-field Hamiltonian and the transient ligand-field Hamiltonian. In the laboratory frame, the bombardment of the complex by solvent molecules causes its Brownian rotation and its vibration-distorsion dynamics governing the fluctuations of the static and transient terms, respectively. These fluctuations are at the origin of electronic relaxation. The electronic relaxation of a Ln(3+) ion is defined by the decays of the time correlation functions (TCFs) of the longitudinal and transverse components of the total angular momentum J of its ground multiplet. The Brownian rotation of the complex and its vibration-distorsion dynamics are simulated by random walks, which enable us to compute the TCFs from first principles. It is shown that the electronic relaxation is governed mainly by the magnitude of the transient ligand-field, and not by its particular expression. The range of expected values of this ligand-field together with the lower limit of relaxation time enforced by the values of the vibration-distortion correlation time in liquids give rise to effective electronic relaxation times which are in satisfactory overall agreement with the experimental data. In particular, these considerations explain why the electronic relaxation times vary little with the coordinating ligand and are practically independent of the external field magnitude. 相似文献
87.
Masae Takahashi Mitsuo Kira Kenkichi Sakamoto Thomas Müller Yitzhak Apeloig 《Journal of computational chemistry》2001,22(13):1536-1541
Vertical electronic transition energies of diaminosilylenes and their dimers (disilenes and nitrogen‐bridged) were investigated by ab initio and density functional calculations. A good linear correlation was found between the observed UV transition energies of various silylenes and disilenes and those of model compounds calculated using the CIS and TD–DFT methods. On the basis of these computations the experimental UV absorption maximum observed for the dimer of (i‐Pr2N)2Si: (λmax 439 nm at 77 K), could be assigned to an Si? Si bonded dimer with an unusually long Si? Si distance of 2.472 Å, and the isomeric amino‐bridged cyclic dimer could be discarded. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1536–1541, 2001 相似文献
88.
Discrete Ti−O−Ti Complexes: Visible-Light-Activated,Homogeneous Alternative to TiO2 Photosensitisers
Kira Behm Dr. Eszter Fazekas Prof. Martin J. Paterson Dr. Filipe Vilela Dr. Ruaraidh D. McIntosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9486-9494
A series of novel bimetallic TiIV amine bis(phenolate) complexes was synthesised and fully characterised. X-ray crystallography studies revealed distorted octahedral geometries around the Ti centres with single or double oxo-bridges connecting the two metals. These robust, air- and moisture-stable complexes were employed as photosensitisers generating singlet oxygen following irradiation with visible light (420 nm) LED module in a commercial flow reactor. All five complexes showed high activity in the photo-oxygenation of α-terpinene and achieved complete conversion to ascaridole in four hours at ambient temperature. The excellent selectivity of these photosensitisers towards ascaridole (vs. transformation to p-cymene) was demonstrated with control experiments using a traditional TiO2 catalyst. Further comparative studies employing the free pro-ligands as well as a monometallic analogue highlighted the importance of the ‘TiO2-like’ moiety in the polymetallic catalysts. Computational studies were used to determine the nature of the ligand to metal charge transfer (LMCT) states and singlet–triplet gaps for each complex, the calculated trends in the UV-vis absorption spectra across the series agreed well with the experimental results. 相似文献
89.
The European Physical Journal C - We give a brief overview of our current theoretical understanding of ultra-relativistic heavy ion collision and the properties of super-hot nuclear matter. We... 相似文献
90.
D. Errede C. Akerlof J. Chapman N. Harnew P. Kesten S. Kooijman D.I. Meyer D. Nitz D. Rubin A.A. Seidl R. Thun T. Trinko M. Willutzky M. Derrick E. Fernandez R. Fries L. Hyman P. Kooijman J. VaVra 《Physics letters. [Part B]》1984,149(6):519-523
A search was made in 29 GeV e+e? annihilations for heavy, neutral leptons decaying to e±X?(ν), where X is a muon or charged meson. Six events with isolated e±X? pairs were found for an intergrated luminosity of 106 pb?1. The expected background is 5.5 ± 2.2 events. Limits on depend on mass and range from 8 to 20 × 10?5 nb. 相似文献