127 resultados para Valence fluctuations.
Resumo:
Mixed valence complexes containing ferro- and ferricyanide have been known for almost 300 years, but no dinuclear, non-polymeric examples of these complexes have been structurally characterized. Here we report the first such example, comprising ferrocyanide coordinated to a pentaaminecobalt(III) complex. This Fe-II-Co-III complex may be reversibly oxidized to the Fe-III-Co-III analogue.
Resumo:
A variable-density groundwater model is used to analyse the effects of tidal fluctuations on sea-water intrusion in an unconfined aquifer. It is shown that the tidal activity forces the sea-water to intrude further inland and it also creates a thicker interface than would occur without tidal effects. Moreover, the configuration of the interface is radically changed when the tidal fluctuations are included. This is because of the dramatic changes in the flow pattern and velocity of the groundwater near the shoreline. For aquifer depths much larger than tidal amplitudes, the tidal fluctuation does not have much effect on how far the sea-water intrudes into the aquifer; nevertheless, a significant change in the configuration of concentration contours because of the effect of tidal fluctuations is observed. This change is more noticeable at the top of the aquifer, near the water table, than at the bottom of the aquifer, and is caused by the infiltration of salt water into the top of the aquifer at higher tidal levels. A flatter beach slope, therefore, intensifies this phenomenon. The interface configurations do not change noticeably over the course of a tidal cycle. Neglecting tidal fluctuation effects results in an inaccurate evaluation of the water table elevation at the land end of the aquifer, although no distinguishable difference is seen between the water tables near the shoreline. Where the landward boundary condition is a constant head, the effects of tidal fluctuations on sea-water intrusion are more pronounced than for cases where the landward boundary condition is a specified flux. Also it is shown that the effects of tidal fluctuations are more significant for a sloping beach than for a vertical shoreline and the salt water intrudes further inland for the sloping case. (C) 1999 Elsevier Science B.V. All rights reserved.
Resumo:
We consider the effect of quantum spin fluctuations on the ground-state properties of the Heisenberg antiferromagnet on an anisotropic triangular lattice using linear spin-wave (LSW) theory. This model should describe the magnetic properties of the insulating phase of the kappa-(BEDT-TTF)(2)X family of superconducting molecular crystals. The ground-state energy, the staggered magnetization, magnon excitation spectra, and spin-wave velocities are computed as functions of the ratio of the antiferromagnetic exchange between the second and first neighbours, J(2)/J(1). We find that near J(2)/J(1) = 0.5, i.e., in the region where the classical spin configuration changes from a Neel-ordered phase to a spiral phase, the staggered magnetization vanishes, suggesting the possibility of a quantum disordered state. in this region, the quantum correction to the magnetization is large but finite. This is in contrast to the case for the frustrated Heisenberg model on a square lattice, for which the quantum correction diverges logarithmically at the transition from the Neel to the collinear phase. For large J(2)/J(1), the model becomes a set of chains with frustrated interchain coupling. For J(2) > 4J(1), the quantum correction to the magnetization, within LSW theory, becomes comparable to the classical magnetization, suggesting the possibility of a quantum disordered state. We show that, in this regime, the quantum fluctuations are much larger than for a set of weakly coupled chains with non-frustrated interchain coupling.
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We consider two different kinds of fluctuations in an ion trap potential: external fluctuating electrical fields, which cause statistical movement (wobbling) of the ion relative to the center of the trap, and fluctuations of the spring constant, which an due to fluctuations of the ac component of the potential applied in the Paul trap for ions. We write down master equations for both cases and, averaging out the noise, obtain expressions for the heating of the ion. We compare our results to previous results for far-off resonance optical traps and heating in ion traps. The effect of fluctuating external electrical fields for a quantum gate operation (controlled-NOT) is determined and the fidelity for that operation derived. [S1050-2947(99)06005-9].
Resumo:
We study the spin-1/2 Heisenberg models on an anisotropic two-dimensional lattice which interpolates between the square lattice at one end, a set of decoupled spin chains on the other end, and the triangular-lattice Heisenberg model in between. By series expansions around two different dimer ground states and around various commensurate and incommensurate magnetically ordered states, we establish the phase diagram for this model of a frustrated antiferromagnet. We find a particularly rich phase diagram due to the interplay of magnetic frustration, quantum fluctuations, and varying dimensionality. There is a large region of the usual two-sublattice Neel phase, a three-sublattice phase for the triangular-lattice model, a region of incommensurate magnetic order around the triangular-lattice model, and regions in parameter space where there is no magnetic order. We find that the incommensurate ordering wave vector is in general altered from its classical value by quantum fluctuations. The regime of weakly coupled chains is particularly interesting and appears to be nearly critical. [S0163-1829(99)10421-1].
Resumo:
The free running linewidth of an external cavity grating feedback diode laser is on the order of a few megahertz and is limited by the mechanical and acoustic vibrations of the external cavity. Such frequency fluctuations can be removed by electronic feedback. We present a hybrid stabilisation technique that uses both a Fabry-Perot confocal cavity and an atomic resonance to achieve excellent short and long term frequency stability. The system has been shown to reduce the laser linewidth of an external cavity diode laser by an order of magnitude to 140 kHz, while limiting frequency excursions to 60 kHz relative to an absolute reference over periods of several hours. The scheme also presents a simple way to frequency offset two lasers many gigahertz apart which should find a use in atom cooling experiments, where hyperfine ground-state frequency separations are often required.
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This paper presents a theoretical model of flow and chemical transport processes in subterranean estuaries (unconfined brackish groundwater aquifers at the ocean-land interface). The model shows that groundwater circulation and oscillating flow, caused by wave setup and tide, may constitute up to 96% of submarine groundwater discharge (SGWD) compared with 4% due to the net groundwater discharge. While these local flow processes do not change the total amount of land-derived chemical input to the ocean over a long period (e.g., yearly), they induce fluctuations of the chemical transfer rate as the aquifer undergoes saltwater intrusion. This may result in a substantial increase in chemical fluxes to the ocean over a short period (e.g., monthly and by a factor of 20 above the averaged level), imposing a possible threat to the marine environment. These results are essentially consistent with the experimental findings of Moore [1996] and have important implications for coastal resources management.
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Groundwater waves, that is, water table fluctuations, are a natural phenomenon in coastal aquifers. They represent an important part of the interaction between the ocean and aquifer and affect the mass exchange between them. This paper presents a new groundwater wave equation. Because it includes the effects of vertical flows and capillarity, the new equation is applicable to both intermediate-depth aquifers and high-frequency waves. Compared with the wave equation derived by Nielsen ed al. [1997], the present equation provides a closer representation of groundwater waves. In particular, it predicts high-frequency water table fluctuations as observed in the field. A validation of the new equation has been carried out by comparing the analytical solutions to it with predictions from direct simulations using the numerical model SUTRA. The effects of various physical parameters and their relative importance are also discussed.
Resumo:
The aim of this paper is to examine distributions of schizophrenia and general population births over time in order to determine whether (a) the pattern has changed over time, (b) any pattern was similar for both males and females, and (c) whether there is any indication that there is any relationship between the changes in pattern between schizophrenia and general population births. Birth month and year for 7807 individuals with ICD8/9 schizophrenia were gained from the Queensland Mental Health Statistical System for 1914-1975. Monthly births for the general population in Queensland for the same period were obtained from the Australian Bureau of Statistics. For each decade we obtained two comparisons, (1) between two 'seasons' (summer-autumn/winter-spring), and (2) between the third (coldest) quarter and the remaining quarters. Based on expected contrasts from general population proportions, odds ratios and their confidence intervals were used to analyse these comparisons for all subjects, and for males and females separately. The seasonality found in our previous studies was again evident (OR 1.09; 95% CI= 1.01-1.17). However there was no significant change in its pattern over time either for the total group or for males and females separately. When the general population births alone were examined using the same contrasts, seasonality was also observed, but here there were fluctuations over time. These results suggest that exposures linked to changes in general population births over time should be examined in disorders such as schizophrenia which demonstrate seasonality in births. The Stanley Foundation supported this project.
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We present a method for measuring single spins embedded in a solid by probing two-electron systems with a single-electron transistor (SET). Restrictions imposed by the Pauli principle on allowed two-electron states mean that the spin state of such systems has a profound impact on the orbital states (positions) of the electrons, a parameter which SET's are extremely well suited to measure. We focus on a particular system capable of being fabricated with current technology: a Te double donor in Si adjacent to a Si/SiO2, interface and lying directly beneath the SET island electrode, and we outline a measurement strategy capable of resolving single-electron and nuclear spins in this system. We discuss the limitations of the measurement imposed by spin scattering arising from fluctuations emanating from the SET and from lattice phonons. We conclude that measurement of single spins, a necessary requirement for several proposed quantum computer architectures, is feasible in Si using this strategy.
Resumo:
Previous studies on tidal dynamics of coastal aquifers have focussed on the inland propagation of oceanic tides in the cross-shore direction, a configuration that is essentially one-dimensional. Aquifers at natural coasts can also be influenced by tidal waves in nearby estuaries, resulting in a more complex behaviour of head fluctuations in the aquifers. We present an analytical solution to the two-dimensional depth-averaged groundwater flow equation for a semi-infinite aquifer subject to oscillating head conditions at the boundaries. The solution describes the tidal dynamics of a coastal aquifer that is adjacent to a cross-shore estuary. Both the effects of oceanic and estuarine tides on the aquifer are included in the solution. The analytical prediction of the head fluctuations is verified by comparison with numerical solutions computed using a standard finite-difference method. An essential feature of the present analytical solution is the interaction between the cross- and along-shore tidal waves in the aquifer area near the estuary's entry. As the distance from the estuary or coastline increases, the wave interaction is weakened and the aquifer response is reduced, respectively, to the one-dimensional solution for oceanic tides or the solution of Sun (Sun H. A two-dimensional analytical solution of groundwater response to tidal loading in an estuary, Water Resour Res 1997;33:1429-35) for two-dimensional non-interacting tidal waves. (C) 2000 Elsevier Science Ltd. All rights reserved.
Resumo:
The title pendent-arm macrocyclic hexaamine ligand binds stereospecifically in a hexadentate manner, and we report here its isomorphous Ni-II and Zn-II complexes (both as perchlorate salts), namely (cis-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine-kappa(6)N)nickel(II) diperchlorate, [Ni(C12H30N6)](ClO4)(2), and (cis-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine-kappa(6)N)zinc(II) diperchlorate, [Zn(C-12 H30N6)](ClO4)(2). Distortion of the N-M-N valence angles from their ideal octahedral values becomes more pronounced with increasing metal-ion size and the present results are compared with other structures of this ligand.
Resumo:
Intracavity and external third order correlations in the damped nondegenerate parametric oscillator are calculated for quantum mechanics and stochastic electrodynamics (SED), a semiclassical theory. The two theories yield greatly different results, with the correlations of quantum mechanics being cubic in the system's nonlinear coupling constant and those of SED being linear in the same constant. In particular, differences between the two theories are present in at least a mesoscopic regime. They also exist when realistic damping is included. Such differences illustrate distinctions between quantum mechanics and a hidden variable theory for continuous variables.
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Rates of cell size increase are an important measure of success during the baculovirus infection process. Batch and fed batch cultures sustain large fluctuations in osmolarity that can affect the measured cell volume if this parameter is not considered during the sizing protocol. Where osmolarity differences between the sizing diluent and the culture broth exist, biased measurements of size are obtained as a result of the cell osmometer response. Spodoptera frugiperda (Sf9) cells are highly sensitive to volume change when subjected to a change in osmolarity. Use of the modified protocol with culture supernatants for sample dilution prior to sizing removed the observed error during measurement.
Resumo:
In quantum measurement theory it is necessary to show how a, quantum source conditions a classical stochastic record of measured results. We discuss mesoscopic conductance using quantum stochastic calculus to elucidate the quantum nature of the measurement taking place in these systems. To illustrate the method we derive the current fluctuations in a two terminal mesoscopic circuit with two tunnel barriers containing a single quasi bound state on the well. The method enables us to focus on either the incoming/ outgoing Fermi fields in the leads, or on the irreversible dynamics of the well state itself. We show an equivalence between the approach of Buttiker and the Fermi quantum stochastic calculus for mesoscopic systems.