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81.
Electrospray ionization mass spectrometry (ESI-MS) is being increasingly employed in the study of metal-ligand equilibria in aqueous solution. In the present work, the ESI-MS spectral changes due to different settings of the following instrumental parameters are analyzed: the solution flow rate (F(S)), the nebulizer gas flow rate (F(G)), the sprayer potential (E), and the temperature of the entrance capillary (T). Twenty-eight spectra were obtained for each of six samples containing aluminum(III) and 2,3-dihydroxypyridine at various pH, in the absence or in the presence of a buffer and of sodium ions. Among the considered instrumental parameters, T produced the largest effects on the ionic intensities. F(S) and F(G) affected the ESI-MS spectra to a lower extent than T. In the investigated conditions E had the weakest effects on the spectra.The correlations observed between the ionic intensities and these instrumental parameters were interpreted considering the presence of three kinds of perturbations occurring in the ESI-MS ion source: formation of some dimers in the droplets, different transfer efficiencies from the droplets to the gas phase for different complexes (according to their surface activity), and subsequent partial thermal decomposition of the dimers and of one of the monomeric complexes in the gas phase. Our results show that the evaluation of the effects produced in the ESI-MS spectra by a change of instrumental parameters can allow to identify the perturbations occurring when metal-ligand solutions are studied by ESI-MS. 相似文献
82.
Valerio Bozza 《General Relativity and Gravitation》2010,42(9):2269-2300
We review the theoretical aspects of gravitational lensing by black holes, and discuss the perspectives for realistic observations.
We will first treat lensing by spherically symmetric black holes, in which the formation of infinite sequences of higher order
images emerges in the clearest way. We will then consider the effects of the spin of the black hole, with the formation of
giant higher order caustics and multiple images. Finally, we will consider the perspectives for observations of black hole
lensing, from the detection of secondary images of stellar sources and spots on the accretion disk to the interpretation of
iron K-lines and direct imaging of the shadow of the black hole. 相似文献
83.
Changjun Gao Youjun Lu You-Gen Shen Valerio Faraoni 《General Relativity and Gravitation》2018,50(1):15
The Hawking–Penrose singularity theorem states that a singularity forms inside a black hole in general relativity. To remove this singularity one must resort to a more fundamental theory. Using a corrected dynamical equation arising in loop quantum cosmology and braneworld models, we study the gravitational collapse of a perfect fluid sphere with a rather general equation of state. In the frame of an observer comoving with this fluid, the sphere pulsates between a maximum and a minimum size, avoiding the singularity. The exterior geometry is also constructed. There are usually an outer and an inner apparent horizon, resembling the Reissner–Nordström situation. For a distant observer the horizon crossing occurs in an infinite time and the pulsations of the black hole quantum “beating heart” are completely unobservable. However, it may be observable if the black hole is not spherical symmetric and radiates gravitational wave due to the quadrupole moment, if any. 相似文献
84.
Lucarini Valerio Ragone Francesco Lunkeit Frank 《Journal of statistical physics》2017,166(3-4):1036-1064
Journal of Statistical Physics - The provision of accurate methods for predicting the climate response to anthropogenic and natural forcings is a key contemporary scientific challenge. Using a... 相似文献
85.
We construct different equivalent non-equilibrium statistical ensembles in a simple yet instructive \(N\) -degrees of freedom model of atmospheric turbulence, introduced by Lorenz in 1996. The vector field can be decomposed into an energy-conserving, time-reversible part, plus a non-time reversible part, including forcing and dissipation. We construct a modified version of the model where viscosity varies with time, in such a way that energy is conserved, and the resulting dynamics is fully time-reversible. For each value of the forcing, the statistical properties of the irreversible and reversible model are in excellent agreement, if in the latter the energy is kept constant at a value equal to the time-average realized with the irreversible model. In particular, the average contraction rate of the phase space of the time-reversible model agrees with that of the irreversible model, where instead it is constant by construction. We also show that the phase space contraction rate obeys the fluctuation relation, and we relate its finite time corrections to the characteristic time scales of the system. A local version of the fluctuation relation is explored and successfully checked. The equivalence between the two non-equilibrium ensembles extends to dynamical properties such as the Lyapunov exponents, which are shown to obey to a good degree of approximation a pairing rule. These results have relevance in motivating the importance of the chaotic hypothesis. in explaining that we have the freedom to model non-equilibrium systems using different but equivalent approaches, and, in particular, that using a model of a fluid where viscosity is kept constant is just one option, and not necessarily the only option, for describing accurately its statistical and dynamical properties. 相似文献
86.
Valerio Lucarini Davide Faranda Jeroen Wouters Tobias Kuna 《Journal of statistical physics》2014,154(3):723-750
In this paper we provide a connection between the geometrical properties of the attractor of a chaotic dynamical system and the distribution of extreme values. We show that the extremes of so-called physical observables are distributed according to the classical generalised Pareto distribution and derive explicit expressions for the scaling and the shape parameter. In particular, we derive that the shape parameter does not depend on the chosen observables, but only on the partial dimensions of the invariant measure on the stable, unstable, and neutral manifolds. The shape parameter is negative and is close to zero when high-dimensional systems are considered. This result agrees with what was derived recently using the generalized extreme value approach. Combining the results obtained using such physical observables and the properties of the extremes of distance observables, it is possible to derive estimates of the partial dimensions of the attractor along the stable and the unstable directions of the flow. Moreover, by writing the shape parameter in terms of moments of the extremes of the considered observable and by using linear response theory, we relate the sensitivity to perturbations of the shape parameter to the sensitivity of the moments, of the partial dimensions, and of the Kaplan–Yorke dimension of the attractor. Preliminary numerical investigations provide encouraging results on the applicability of the theory presented here. The results presented here do not apply for all combinations of Axiom A systems and observables, but the breakdown seems to be related to very special geometrical configurations. 相似文献
87.
X‐ray‐excited optical luminescence (XEOL) emission and excitation spectra as well as the EXAFS signal of CdWO4 were measured in the energy region of the Cd and W absorption edges. From EXAFS refinement, structural parameters such as number of atoms, distance from the absorbing atom and width of coordination shells in the W neighborhood were determined. The role of W–O interactions on the intrinsic luminescence of CdWO4 is discussed. The efficiencies of conversion, transfer and emission processes involved in the scintillation mechanism showed to be high when self‐trapped excitons are formed locally by direct excitation of W ions. Annihilation of these excitons provides the characteristic scintillation of CdWO4, a broad band emission with maximum at 500 nm. The presence of two energetically different O positions in the lattice gives rise to the composite structure of the luminescence band, and no influence of extrinsic defects was noticed. A mismatch between the X‐ray absorption coefficient and the zero‐order luminescence curves corroborates that the direct excitation of Cd ions induces secondary electronic excitations not very effective in transferring energy to the luminescent group, WO6. 相似文献
88.
In this paper, we perform an analytical and numerical study of the extreme values of specific observables of dynamical systems possessing an invariant singular measure. Such observables are expressed as functions of the distance of the orbit of initial conditions with respect to a given point of the attractor. Using the block maxima approach, we show that the extremes are distributed according to the generalised extreme value distribution, where the parameters can be written as functions of the information dimension of the attractor. The numerical analysis is performed on a few low dimensional maps. For the Cantor ternary set and the Sierpinskij triangle, which can be constructed as iterated function systems, the inferred parameters show a very good agreement with the theoretical values. For strange attractors like those corresponding to the Lozi and He?non maps, a slower convergence to the generalised extreme value distribution is observed. Nevertheless, the results are in good statistical agreement with the theoretical estimates. It is apparent that the analysis of extremes allows for capturing fundamental information of the geometrical structure of the attractor of the underlying dynamical system, the basic reason being that the chosen observables act as magnifying glass in the neighborhood of the point from which the distance is computed. 相似文献
89.
Hawking has proven that black holes which are stationary as the end point of gravitational collapse in Brans-Dicke theory (without a potential) are no different than in general relativity. We extend this proof to the much more general class of scalar-tensor and f(R) gravity theories, without assuming any symmetries apart from stationarity. 相似文献
90.
Koichi Todoroki Maurizio Corradini Ryugo S. Hayano Takumi Kobayashi Marco Leali Evandro Lodi Rizzini Valerio Mascagna Anna Soter Luca Venturelli Nicola Zurlo Masaki Hori 《Hyperfine Interactions》2012,213(1-3):199-204
The ASACUSA (the Atomic Spectroscopy And Collisions Using Slow Antiprotons) collaboration is planning to measure the cross sections of antiproton annihilations at kinetic energy 100 keV on targets of various mass numbers (C,?Ni, Sn, and Pt) using the Antiproton Decelerator (AD) of CERN. No previous measurement exists in this region where the A-dependence of the cross section is expected to deviate from the A $^{\frac{2}{3}}$ (Batty et al, Nucl Phys A 689:721, 2001) as reported by the Obelix collaboration. A beam profile monitor based on secondary electron emission with a grid of electrode pads fabricated on an FR4-type glass-epoxy circuit board was developed for this measurement. The advantage of this kind of detector is that it is simple, lightweight, and low cost. It was used to measure the spatial profile of 100-ns-long beam pulses containing > 6 × 104 antiprotons with an active area of 40?mm?× 40 mm and a spatial resolution of 4 mm. 相似文献