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91.
92.
Loumaigne M Vasanthakumar P Richard A Débarre A 《Physical chemistry chemical physics : PCCP》2011,13(24):11597-11605
The Brownian rotation of a nearly spherical gold particle capped with ligands can be observed in the correlation profile of the intensity of the two-photon excited luminescence. Here we report on a multi-parameter study of the luminescence properties, including spectral and polarization analysis of the signal at the single particle level. First, the data confirm the role of the radiative de-excitation of the surface plasmons in the luminescence process. Secondly, the results obtained at low power indicate that the capped particle in water can be approximatively described as a spherical rotor acting in the far-field as a point-like absorption and emission dipole of fixed directions. In addition, we show that the dynamics of the ligands, induced by the heat transfer from the particle to its environment, can be partly controlled by the choice of excitation wavelength. 相似文献
93.
Cross sections and rate coefficients for low lying rotational transitions in HDO induced by para and ortho-H(2) collisions are presented for the first time. Calculations have been performed at the close-coupling and coupled-states levels with the deuterated variant of the H(2)O-H(2) interaction potential of Valiron et al. [J. Chem. Phys., 2008, 129, 134306]. Rate coefficients are presented for temperatures between 5 and 100 K and are compared to the corresponding rates for H(2)O and D(2)O. Significant differences caused by the isotopic substitution, in particular the C(2v) symmetry breaking, are observed. Finally, our rates are found to be significantly larger (by up to three orders of magnitude at 50 K) than the corresponding HDO-He rates and should lead to a thorough re-estimation of the abundance of interstellar HDO. 相似文献
94.
Steichen M Thomassey M Siebentritt S Dale PJ 《Physical chemistry chemical physics : PCCP》2011,13(10):4292-4302
The electrochemical deposition of Ga and Cu-Ga alloys from the deep eutectic solvent choline chloride/urea (Reline) is investigated to prepare CuGaSe(2) (CGS) semiconductors for their use in thin film solar cells. Ga electrodeposition is difficult from aqueous solution due to its low standard potential and the interfering hydrogen evolution reaction (HER). Ionic liquid electrolytes offer a better thermal stability and larger potential window and thus eliminate the interference of solvent breakdown reactions during Ga deposition. We demonstrate that metallic Ga can be electrodeposited from Reline without HER interference with high plating efficiency on Mo and Cu electrodes. A new low cost synthetic route for the preparation of CuGaSe(2) absorber thin films is presented and involves the one-step electrodeposition of Cu-Ga precursors from Reline followed by thermal annealing. Rotating disk electrode (RDE) cyclic voltammetry (CV) is used in combination with viscosity measurements to determine the diffusion coefficients of gallium and copper ions in Reline. The composition of the codeposited Cu-Ga precursor layers can be controlled to form Cu/Ga thin films with precise stoichiometry, which is important for achieving good optoelectronic properties of the final CuGaSe(2) absorbers. The morphology, the chemical composition and the crystal structure of the deposited thin films are analysed by scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX) and X-ray diffraction (XRD). Annealing of the Cu-Ga films in a selenium atmosphere allowed the formation of high quality CuGaSe(2) absorber layers. Completed CGS solar cells achieved a 4.1% total area power conversion efficiency. 相似文献
95.
The predictive capabilities of the shear-modified Gurson model [Nielsen and Tvergaard, Eng. Fract. Mech. 77, 2010] and the Modified Mohr-Coulomb (MMC) fracture model [Bai and Wierzbicki, Int. J. Fract. 161, 2010] are evaluated. Both phenomenological fracture models are physics-inspired and take the effect of the first and third stress tensor invariants into account in predicting the onset of ductile fracture. The MMC model is based on the assumption that the initiation of fracture is determined by a critical stress state, while the shear-modified Gurson model assumes void growth as the governing mechanism. Fracture experiments on TRIP-assisted steel sheets covering a wide range of stress states (from shear to equibiaxial tension) are used to calibrate and validate these models. The model accuracy is quantified based on the predictions of the displacement to fracture for experiments which have not been used for calibration. It is found that the MMC model predictions agree well with all experiments (less than 4% error), while less accurate predictions are observed for the shear-modified Gurson model. A comparison of plots of the strain to fracture as a function of the stress triaxiality and the normalized third invariant reveals significant differences between the two models except within the vicinity of stress states that have been used for calibration. 相似文献
96.
97.
Lan Liu Robert B. Pansu Jean Faure Jacques Roncin Bernard Arrio René Lapouyade 《Research on Chemical Intermediates》1995,21(7):765-775
The phase transition of dihexadecyl phosphate (DHP) bilayered disks has been studied using EPR spectroscopy. In the acid form
of DHP, a phase transition temperature exists, that we have monitored through the spin-spin interaction between the nitroxide
molecules at high concentration (8%) in DHP bilayers. This spin-spin interaction is due to the gathering of solutes in a fluid
defect of the membrane: the border. The fluorescence quenching of two probes by the nitroxide stearic acids in DHP bilayers
has been studied by stationary and time-resolved fluorescence measurements. The quenching process is mainly static. Both magnetic
and fluorescent probes are localized in the periphery of the bilayered disks.
An erratum to this article is available at . 相似文献
98.
In design optimization and parameter identification, the objective, or response function(s) are typically linked to the actually independent variables through equality constraints, which we will refer to as state equations. Our key assumption is that it is impossible to form and factor the corresponding constraint Jacobian, but one has instead some fixed-point algorithm for computing a feasible state, given any reasonable value of the independent variables. Assuming that this iteration is eventually contractive, we will show how reduced gradients (Jacobians) and Hessians (in other words, the total derivatives) of the response(s) with respect to the independent variables can be obtained via algorithmic, or automatic, differentiation (AD). In our approach the actual application of the so-called reverse, or adjoint differentiation mode is kept local to each iteration step. Consequently, the memory requirement is typically not unduly enlarged. The resulting approximating Lagrange multipliers are used to compute estimates of the reduced function values that can be shown to converge twice as fast as the underlying state space iteration. By a combination with the forward mode of AD, one can also obtain extra-accurate directional derivatives of the reduced functions as well as feasible state space directions and the corresponding reduced or projected Hessians of the Lagrangian. Our approach is verified by test calculations on an aircraft wing with two responses, namely, the lift and drag coefficient, and two variables, namely, the angle of attack and the Mach number. The state is a 2-dimensional flow field defined as solution of the discretized Euler equation under transonic conditions. 相似文献
99.
R. Faure J. P. Galy G. Giusti E. J. Vincent J. Elguero 《Magnetic resonance in chemistry : MRC》1974,6(9):485-486
Azido-tetrazole equilibrium is observed in the case of a solution of tetrazolo [5,1-b] benzothiazole in CDCl3, using proton magnetic resonance at 250 MHz. Analysis of the spectra obtained yields the chemical shifts and the coupling constants of the two tautomeric forms. 相似文献
100.