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71.
Alia JD Vlaisavljevich B Abbot M Warneke H Mastin T 《The journal of physical chemistry. A》2008,112(40):9784-9795
Structurally covariant valency interaction formulas, VIF, gain chemical significance by comparison with resonance structures and natural bond orbital, NBO, bonding schemes and at the same time allow for additional prediction such as symmetry of ring systems and destabilization of electron pairs with respect to reference energy of -1/2 Eh. Comparisons are based on three chemical interpretations of Sinano?lu's theory of structural covariance: (1) sets of structurally covariant quantum structural formulas, VIF, are interpreted as the same quantum operator represented in linearly related basis frames; (2) structurally covariant VIF pictures are interpreted as sets of molecular species with similar energy; and (3) the same VIF picture can be interpreted as different quantum operators, one-electron density or Hamiltonian; for example. According to these three interpretations, bond pair, lone pair, and free radical electrons understood in terms of a localized orbital representation are recognized as having energies above, below, or equal to a predetermined reference, frequently-1/2 Eh. The probable position of electron pairs and radical electrons is predicted. The selectivity of concerted ring closures in allyl anion and cation is described. Symmetries of conjugated ring systems are predicted according to their numbers of pi-electrons and spin-multiplicity. The pi-distortivity of benzene is predicted.The 3c/2e- H-bridging bonds in diborane are derived in a natural way according to the notion that the bridging bonds will have delocalizing interactions between them consistent with results of the NBO method. Key chemical bonding motifs are described using VIF. These include 2c/1e-, 2c/2e-, 2c/3e-, 3c/2e-, 3c/3e-,3c/4e-, 4n antiaromatic, and 4n+2 aromatic bonding systems. Some common organic functional groups are represented as VIF pictures and because these pictures can be interpreted simultaneously as one-electron density and Hamiltonian operators, the valence shell electron pair repulsion method is applied toward understanding the energies of valence NBOs with respect to the reference energy of -1/2Eh. 相似文献
72.
Crouse CA Maruyama B Colorado R Back T Barron AR 《Journal of the American Chemical Society》2008,130(25):7946-7954
Carbon nanotubes (CNTs) have been grown using Fe, Co, Ni, and Co/Fe spin-on-catalyst (SOC) systems, involving the metal salt dispersed with a spin-on-glass precursor. During initial growth runs (CH4/H2/900 degrees C), the CNT yield followed the order Co-SOC > Fe-SOC > Ni-SOC. The Fe catalysts produced the longest nanotubes at the expense of a larger average CNT diameter and broader diameter distribution than the Co-SOC system. A series of Co/Fe-SOCs were prepared where as the atomic percentage of Co is increased nucleation of CNT increases but the CNT length decreases. The linear relationship between the diameter and length of CNTs grown from the Co/Fe-SOC suggests that slow growth is beneficial with respect to control over CNT diameter. After initial CNT growth, the original samples were subjected to additional growth runs. Four individual reactions were observed in the Fe-SOC and binary Co/Fe-SOC: regrowth (amplification), double growth (a second CNT growing from a previously active catalyst), CNT etching, and nucleation from initially inactive catalysts (new growth). CNT etching was observed for the mixed catalyst systems (Co/Fe-SOC) but not for either Fe-SOC or Co-SOC. During the regrowth experiments, CNTs were observed that were not present after the initial growth run (and were not as a result of amplification or double growth). Thus, catalysts, which were initially inactive toward nucleation of CNTs in the original growth run, are capable of becoming activated when placed back into the furnace and submitted to regrowth under identical conditions. 相似文献
73.
Synchrotron X‐ray CT characterization of titanium parts fabricated by additive manufacturing. Part I. Morphology
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Nicola Vivienne Yorke Scarlett Peter Tyson Darren Fraser Sheridan Mayo Anton Maksimenko 《Journal of synchrotron radiation》2016,23(4):1006-1014
Synchrotron X‐ray tomography has been applied to the study of titanium parts fabricated by additive manufacturing (AM). The AM method employed here was the Arcam EBM® (electron beam melting) process which uses powdered titanium alloy, Ti64 (Ti alloy with approximately 6%Al and 4%V), as the feed and an electron beam for the sintering/welding. The experiment was conducted on the Imaging and Medical Beamline of the Australian Synchrotron. Samples were chosen to examine the effect of build direction and complexity of design on the surface morphology and final dimensions of the piece. 相似文献
74.
Let L be a homogeneous left-invariant differential operator on a Carnot group. Assume that both L and Lt are hypoelliptic. We study the removable sets for L-solutions. We give precise conditions in terms of the Carnot- Caratheodory Hausdorff dimension for the removability for L-solutions under several auxiliary integrability or regularity hypotheses. In some cases, our criteria are sharp on the level of the relevant Hausdorff measure. One of the main ingredients in our proof is the use of novel local self-similar tilings in Carnot groups. 相似文献
75.
Bert O. Baumgaertner Rebecca C. Tyson Stephen M. Krone 《The Journal of mathematical sociology》2016,40(4):207-218
Opinions are rarely binary; they can be held with different degrees of conviction, and this expanded attitude spectrum can affect the influence one opinion has on others. Our goal is to understand how different aspects of influence lead to recognizable spatio-temporal patterns of opinions and their strengths. To do this, we introduce a stochastic spatial agent-based model of opinion dynamics that includes a spectrum of opinion strengths and various possible rules for how the opinion strength of one individual affects the influence that this individual has on others. Through simulations, we find that even a small amount of amplification of opinion strength through interaction with like-minded neighbors can tip the scales in favor of polarization and deadlock. 相似文献
76.
Back DF de Oliveira GN Burrow RA Castellano EE Abram U Lang ES 《Inorganic chemistry》2007,46(7):2356-2358
The reaction of Hg(TePh)2 with AgX (X = Cl, NO3) in the presence of PPh3 and PMePh2 in dimethylformamide (DMF) affords the cluster [Hg6Ag4(TePh)16] (1) at room temperature or [Hg6Ag4Te(TePh)14]2 (2) with heating. When Hg(TePh)2 is reacted with [Co(PPh3)2Cl2] or [Ni(PPh3)2Cl2], the clusters [Hg8Te(PhTe)12Cl4]Q [3; Q = [Co(DMF)6]2+ (3a), [Ni(DMF)6]2+ (3b)] are formed. The syntheses of 1 and 2 occur with the incorporation of AgI into the cluster, and the single-crystal analyses show that the two ternary clusters consist of Hg, Ag, and Te centers occupying well-defined positions. Compounds 3a and 3b do not show the incorporation of the metal into the cluster, but the CoII and NiII salts provide the Cl atom to generate the anionic cluster 3 stabilized by the [Co(DMF)6]2+ or [Ni(DMF)6]2+ ion. 相似文献
77.
Ni(II) complexation to amorphous hydrous ferric oxide: an X-ray absorption spectroscopy study 总被引:2,自引:0,他引:2
Xu Y Axe L Boonfueng T Tyson TA Trivedi P Pandya K 《Journal of colloid and interface science》2007,314(1):10-17
Ni(II) sorption onto iron oxides and in particular hydrous ferric oxide (HFO) is among the important processes impacting its distribution, mobility, and bioavailability in environment. To develop mechanistic models for Ni, extended X-ray absorption fine structure (EXAFS) analysis has been conducted on Ni(II) sorbed to HFO. Coprecipitation revealed the formation of the metastable alpha-Ni(OH)(2) at a Ni(II) loading of 3.5 x 10(-3) molg(-1). On the other hand, Ni(II) formed inner-sphere mononuclear bidentate complexes along edges of FeO(6) octahedra when sorbed to HFO surfaces with Ni-O distances of 2.05-2.07 A and Ni-Fe distances of 3.07-3.11 A. This surface complex was observed by EXAFS study over 2.8 x 10(-3) to 10(-1) ionic strength, pH from 6 to 7, a Ni(II) loading of 8 x 10(-4) to 8.1 x 10(-3) molg(-1) HFO, and reaction times from 4 hours to 8 months. The short- and long-range structure analyses suggest that the presence of Ni(II) inhibited transformation of the amorphous iron oxide into a more crystalline form. However, Ni(2+) was not observed to substitute for Fe(3+) in the oxide structure. This study systematically addresses Ni(II) adsorption mechanisms to amorphous iron oxide. The experimentally defined surface complexes can be used to constrain surface complexation modeling for improved prediction of metal distribution at the iron oxide/aqueous interface. 相似文献
78.
The cyclization of gamma-chloroamine 11, derived from l-alanine, and acetylenic sulfone 12 afforded the dehydropiperidine 19 via conjugate addition followed by intramolecular alkylation of the corresponding sulfone-stabilized anion. An unexpected acid-catalyzed desulfonylation of 19 occurred in one step via desilylation and tautomerization of the enamine moiety to the corresponding aldehyde, followed by elimination of p-toluenesulfinic acid. The highly stereoselective reduction of the resulting unsaturated aldehyde 25 with sodium cyanoborohydride produced piperidine 23 with a diastereomeric ratio of >98:2. (-)-(ent)-Julifloridine (8) was obtained by Swern oxidation of 23, followed by Wittig olefination and hydrogenation/debenzylation. 相似文献
79.
E. Heindl C. Kefes M. Soda J. Vancea C.H. Back 《Journal of magnetism and magnetic materials》2009,321(22):3693-3697
We investigate spin-dependent hot electron transport through metallic epitaxial spin valves by ballistic electron magnetic microscopy (BEMM). By variation of the thickness of one of the ferromagnetic layers we determine the spin dependent attenuation lengths which reflect hot electron transport along the vicinity of the [1 0 0]-axis of the bcc Fe34Co66 lattice. The majority spin attenuation length is more than 6 times larger than that of the minority spins within the measured energy interval of 1.3 up to 2 eV above the Fermi level. Consequently a Magnetocurrent effect exceeding 1200% accompanied by a monotonic bias voltage behavior is observed at room temperature. 相似文献