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121.
Miraj Shah Maciej Wojdak Anthony J. Kenyon Matthew P. Halsall Hang Li Iain F. Crowe 《Journal of luminescence》2012,132(12):3103-3112
Erbium doped silicon-rich silica offers broad band and very efficient excitation of erbium photoluminescence (PL) due to a sensitization effect attributed to silicon nanocrystals (Si-nc), which grow during thermal treatment. PL decay lifetime measurements of sensitised Er3+ ions are usually reported to be stretched or multi exponential, very different to those that are directly excited, which usually show a single exponential decay component.In this paper, we report on SiO2 thin films doped with Si-nc's and erbium. Time resolved PL measurements reveal two distinct 1.54 μm Er decay components; a fast microsecond component, and a relatively long lifetime component (10 ms). We also study the structural properties of these samples through TEM measurements, and reveal the formation of Er clusters. We propose that these Er clusters are responsible for the fast μs decay component, and we develop rate equation models that reproduce the experimental transient observations, and can explain some of the reported transient behaviour in previously published literature. 相似文献
122.
We study the partition function of the Potts model in an external (magnetic) field, and its connections with the zero-field
Potts model partition function. Using a deletion-contraction formulation for the partition function Z for this model, we show that it can be expanded in terms of the zero-field partition function. We also show that Z can be written as a sum over the spanning trees, and the spanning forests, of a graph G. Our results extend to Z the well-known spanning tree expansion for the zero-field partition function that arises though its connections with the
Tutte polynomial. 相似文献
123.
124.
DD Schnaars AJ Gaunt TW Hayton MB Jones I Kirker N Kaltsoyannis I May SD Reilly BL Scott G Wu 《Inorganic chemistry》2012,51(15):8557-8566
A series of tetravalent An(IV) complexes with a bis-phenyl β-ketoiminate N,O donor ligand has been synthesized with the aim of identifying bonding trends and changes across the actinide series. The neutral molecules are homoleptic with the formula An((Ar)acnac)(4) (An = Th (1), U (2), Np (3), Pu (4); (Ar)acnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-(t)Bu(2)C(6)H(3)) and were synthesized through salt metathesis reactions with actinide chloride precursors. NMR and electronic absorption spectroscopy confirm the purity of all four new compounds and demonstrate stability in both solution and the solid state. The Th, U, and Pu complexes were structurally elucidated by single-crystal X-ray diffraction and shown to be isostructural in space group C2/c. Analysis of the bond lengths reveals shortening of the An-O and An-N distances arising from the actinide contraction upon moving from 1 to 2. The shortening is more pronounced upon moving from 2 to 4, and the steric constraints of the tetrakis complexes appear to prevent the enhanced U-O versus Pu-O orbital interactions previously observed in the comparison of UI(2)((Ar)acnac)(2) and PuI(2)((Ar)acnac)(2) bis-complexes. Computational analysis of models for 1, 2, and 4 (1a, 2a, and 4a, respectively) concludes that both the An-O and the An-N bonds are predominantly ionic for all three molecules, with the An-O bonds being slightly more covalent. Molecular orbital energy level diagrams indicate the largest 5f-ligand orbital mixing for 4a (Pu), but spatial overlap considerations do not lead to the conclusion that this implies significantly greater covalency in the Pu-ligand bonding. QTAIM bond critical point data suggest that both U-O/U-N and Pu-O/Pu-N are marginally more covalent than the Th analogues. 相似文献
125.
Muoniated radicals were produced by the addition of muonium (Mu) to the aromatic compound p-xylene (1) in the solid and liquid states and to the strained aromatic compound [2.2]paracyclophane (2) in the solid state. The radicals were characterized by avoided level crossing muon spin resonance spectroscopy and identified by comparing the experimentally determined muon hyperfine coupling constants with values obtained from DFT calculations. Mu was observed to add to both the secondary and tertiary carbons of 1, with the relative yield of the Mu adduct of the tertiary carbons estimated to be ~10% in the liquid phase. The relative yield of the tertiary adduct is much higher in the solid state although this cannot be calculated exactly due to the overlap of resonances and the apparent nonuniform distribution of the radical orientations. There are three possible addition sites in 2 due to the lower symmetry of the six-membered ring compared with 1. Mu can add to the secondary carbons either from the outside of 2, generating the "exo" adduct, or from the inside, generating the "endo" adduct. The relative yields of the exo, endo, and tertiary carbon adducts are 67.1(1), 21.8(1), and 11.1(1)%, respectively. The barriers to Mu addition at the different sites of isolated molecules were determined from DFT calculations. The barriers for Mu addition to 2 are lower than the barriers for Mu addition to 1, except for addition to the "endo" position, where the unfavorable steric interactions with the second ring of 2 raise the addition barrier considerably. The measured relative yields do not reflect the distribution of products calculated using the activation energies obtained from the DFT calculations due to strong steric interactions with neighboring molecules. 相似文献
126.
Significance of grafting in curing processes initiated by UV, excimer and ionising radiation sources
John L. Garnett Loo-Teck Ng Visay Viengkhou Iain W. Hennessy Elvis F. Zilic 《Radiation Physics and Chemistry》2000,57(3-6):355-359
The grafting of a typical methacrylate monomer (MMA) to polypropylene (PPE) and cellulose initiated by UV and ionising radiation is reported. The effect of additives which constitute components in radiation curing on the grafting process is examined. Additives studied include photoinitiators (PIs), multifunctional acrylates and methacrylates and acrylate oligomers. Synergistic effects when these additives are combined in the same solution are reported. The photografting studies have been extended to include grafting with charge transfer (CT) complexes involving donor/acceptor (DA) monomers to PPE, cellulose and wool. The importance of this work in conventional and PI free curing is discussed, particularly the significance of concurrent grafting during curing. 相似文献
127.
Planar bilayer lipid membranes (BLMs) are currently employed to construct many bio-inspired material systems and structures. In order to characterize the pressure effects on the equilibrium configurations of these biological membranes, a novel continuum model is proposed. The BLM is assumed to be a two-layer Smectic A liquid crystal. The mean orientation of the amphiphilic molecules comprising the membrane is postulated to be perpendicular to the layers and each layer is idealized as a two dimensional liquid. Moreover, the BLM is modeled as a simply supported plate undergoing small deformations. It is subjected to a pressure load that acts perpendicularly to the layers. The equilibrium equations and boundary conditions are derived from the bulk elastic energy for Smectic A liquid crystals as described by de Gennes and Prost (1993) by using variational methods. The resulting fourth-order linear partial differential equation is solved by employing cylindrical functions and the series solution is proved to be convergent. The solution is numerically computed for values of the model parameters that are reported in the literature. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
128.
液相色谱-紫外-核磁共振-质谱:多信息分离方法 总被引:2,自引:0,他引:2
The availability of liquid chromatography-uhraviolet-nuclear magnetic reso-nance-mass spectrometry (LC-UV-NMR-MS)integrated systems is providing greater information content and confidence for a variety of sample types, such asdrug metabolites,natural products, impurities, and degradants. A wide range of experimental strategiescan be pur-sued,highlighting the flexibility and performance possible with this multihyphenated technique. 相似文献
129.
<正>Organic electronic applications require a combination of low-cost fabrication methods and features such as mechanical flexibility that are not achievable with inorganic materials. Both organic small molecule and polymer semiconductors offer the potential to deliver a new range of consumer applications, enabled by the unique benefits of these classes of materials [1]. Polymers in particular are attractive materials, offering potentially low cost synthesis and 相似文献
130.
Alessia Petti Matthew C. Leech Anthony D. Garcia Iain C. A. Goodall Adrian P. Dobbs Kevin Lam 《Angewandte Chemie (International ed. in English)》2019,58(45):16115-16118
A new electrochemical methodology has been developed for the generation of oxycarbonyl radicals under mild and green conditions from readily available hemioxalate salts. Mono‐ and multi‐functionalised γ‐butyrolactones were synthesised through exo‐cyclisation of these oxycarbonyl radicals with an alkene, followed by the sp3–sp3 capture of the newly formed carbon‐centred radical. The synthesis of functionalised valerolactone derivatives was also achieved, demonstrating the versatility of the newly developed methodology. This represents a viable synthetic route towards pharmaceutically important fragments and further demonstrates the practicality of electrosynthesis as a green and economical method to activate small organic molecules. 相似文献