Oxidation of mixed-valence CoIII/FeII complexes reversed at high pH: A kinetico-mechanistic study of water oxidation

The outer-sphere oxidation of Fell in the mixed-valence complex trans-[(LCoNCFeII)-Co-14S-N-III(CN)(6)](-), being L-14S an N3S2 macrocylic donor set on the cobalt(III) center, has been studied. The comparison with the known processes of N-5 macrocycle complexes has been carried out in view of the important differences occurring on the redox potential of the cobalt center. The results indicate that the outer-sphere oxidation reactions with S2O82- and [Co(ox)(3)](3-) involve a great amount of solvent-assisted hydrogen bonding that, as a consequence from the change from two amines to sulfur donors, are more restricted. This is shown by the more positive values found for DeltaS(double dagger) and DeltaV(double dagger). The X-ray structure of the oxidized complex has been determined, and it is clearly indicative of the above-mentioned solvent-assisted hydrogen bonding between nitrogen and cyanide donors on the cobalt and iron centers, respectively. trans-[(LCoNCFeIII)-Co-14S-N-III(CN)(6)], as well as the analogous N-5 systems trans-[(LCoNCFeIII)-Co-14-N-III(CN)(6)], trans-[(LCoNCFeIII)-Co-15-N-III-(CN)(6)], and cis-[(LCoNCFeIII)-Co-n-N-III(CN)(6)], Oxidize water to hydrogen peroxide at pH > 10 with a rather simple stoichiometry, i.e., [(LCoNCFeIII)-Co-n-N-III(CN)(5)] + OH- - [(LCoNCFeII)-Co-n-N-III(CN)(5)](-) + 1/2H(2)O(2). In this way, the reversibility of the iron oxidation process is achieved. The determination of kinetic and thermal and pressure activation parameters for this water to hydrogen peroxide oxidation leads to the kinetic determination of a cyanide based OH- adduct of the complex. A second-order dependence on the base concentration is associated with deprotonation of this adduct to produce the final inner-sphere reduction process. The activation enthalpies are found to be extremely low (15 to 35 kJ mol(-1)) and responsible for the very fast reaction observed. The values of DeltaS(double dagger) and DeltaV(double dagger) (-76 to -113 J K-1 mol(-1) and -5.5 to -8.9 cm(3) mol(-1), respectively) indicate a highly organized but not very compressed transition state in agreement with the inner-sphere one-electron transfer from O2- to Fe-III.

Experimental characterization of continuous-variable entanglement

We present an experimental analysis of quadrature entanglement produced from a pair of amplitude squeezed beams. The correlation matrix of the state is characterized within a set of reasonable assumptions, and the strength of the entanglement is gauged using measures of the degree of inseparability and the degree of Einstein-Podolsky-Rosen (EPR) paradox. We introduce controlled decoherence in the form of optical loss to the entangled state, and demonstrate qualitative differences in the response of the degrees of inseparability and EPR paradox to this loss. The entanglement is represented on a photon number diagram that provides an intuitive and physically relevant description of the state. We calculate efficacy contours for several quantum information protocols on this diagram, and use them to predict the effectiveness of our entanglement in those protocols.

The effect of finite bandwidth squeezed light on entanglement creation in the Dicke model

We analyse the relation between local two-atom and total multi-atom entanglements in the Dicke system composed of a large number of atoms. We use concurrence as a measure of entanglement between two atoms in the multi-atom system, and the spin squeezing parameter as a measure of entanglement in the whole n-atom system. In addition, the influence of the squeezing phase and bandwidth on entanglement in the steady-state Dicke system is discussed. It is shown that the introduction of a squeezed field leads to a significant enhancement of entanglement between two atoms, and the entanglement increases with increasing degree of squeezing and bandwidth of the incident squeezed field. In the presence of a coherent field the entanglement exhibits a strong dependence on the relative phase between the squeezed and coherent fields, that can jump quite rapidly from unentangled to strongly entangled values when the phase changes from zero to pi. We find that the jump of the degree of entanglement is due to a flip of the spin squeezing from one quadrature component of the atomic spin to the other component when the phase changes from zero to pi. We also analyse the dependence of the entanglement on the number of atoms and find that, despite the reduction in the degree of entanglement between two atoms, a large entanglement is present in the whole n-atom system and the degree of entanglement increases as the number of atoms increases.

Transmission of optical coherent-state qubits

We discuss the long-distance transmission of qubits encoded in optical coherent states. Through absorption, these qubits suffer from two main types of errors, namely the reduction of the amplitude of the coherent states and accidental application of the Pauli Z operator. We show how these errors can be fixed using techniques of teleportation and error-correcting codes.

Energy as an entanglement witness for quantum many-body systems

We investigate quantum many-body systems where all low-energy states are entangled. As a tool for quantifying such systems, we introduce the concept of the entanglement gap, which is the difference in energy between the ground-state energy and the minimum energy that a separable (unentangled) state may attain. If the energy of the system lies within the entanglement gap, the state of the system is guaranteed to be entangled. We find Hamiltonians that have the largest possible entanglement gap; for a system consisting of two interacting spin-1/2 subsystems, the Heisenberg antiferromagnet is one such example. We also introduce a related concept, the entanglement-gap temperature: the temperature below which the thermal state is certainly entangled, as witnessed by its energy. We give an example of a bipartite Hamiltonian with an arbitrarily high entanglement-gap temperature for fixed total energy range. For bipartite spin lattices we prove a theorem demonstrating that the entanglement gap necessarily decreases as the coordination number is increased. We investigate frustrated lattices and quantum phase transitions as physical phenomena that affect the entanglement gap.

Quantum entanglement and fixed-point bifurcations

How does the classical phase-space structure for a composite system relate to the entanglement characteristics of the corresponding quantum system? We demonstrate how the entanglement in nonlinear bipartite systems can be associated with a fixed-point bifurcation in the classical dynamics. Using the example of coupled giant spins we show that when a fixed point undergoes a supercritical pitchfork bifurcation, the corresponding quantum state-the ground state-achieves its maximum amount of entanglement near the critical point. We conjecture that this will be a generic feature of systems whose classical limit exhibits such a bifurcation.

Entanglement and the Einstein-Podolsky-Rosen paradox with coupled intracavity optical down-converters

We show that two evanescently coupled χ((2)) parametric down-converters inside a Fabry-Perot cavity provide a tunable source of quadrature squeezed light, Einstein-Podolsky-Rosen (EPR) correlations and quantum entanglement. Analyzing the operation in the below threshold regime, we show how these properties can be controlled by adjusting the coupling strengths and the cavity detunings. As this can be implemented with integrated optics, it provides a possible route to rugged and stable EPR sources.

Modulating the rate and rhythmicity of perceptual rivalry alternations with the mixed 5-HT2A and 5-HT1A agonist psilocybin

Binocular rivalry occurs when different images are presented simultaneously to corresponding points within the left and right eyes. Under these conditions, the observer's perception will alternate between the two perceptual alternatives. Motivated by the reported link between the rate of perceptual alternations, symptoms of psychosis and an incidental observation that the rhythmicity of perceptual alternations during binocular rivalry was greatly increased 10 h after the consumption of LSD, this study aimed to investigate the pharmacology underlying binocular rivalry and to explore the connection between the timing of perceptual switching and psychosis. Psilocybin (4-phosphoryloxy-N,N-dimethyltryptamine, PY) was chosen for the study because, like LSD, it is known to act as an agonist at serotonin (5-HT)(1A) and 5-HT2A receptors and to produce an altered state sometimes marked by psychosis-like symptoms. A total of 12 healthy human volunteers were tested under placebo, low-dose ( 115 mg/kg) and high-dose ( 250 mg/kg) PY conditions. In line with predictions, under both low- and high-dose conditions, the results show that at 90 min postadministration ( the peak of drug action), rate and rhythmicity of perceptual alternations were significantly reduced from placebo levels. Following the 90 min testing period, the perceptual switch rate successively increased, with some individuals showing increases well beyond pretest levels at the final testing, 360 min postadministration. However, as some subjects had still not returned to pretest levels by this time, the mean phase duration at 360 min was not found to differ significantly from placebo. Reflecting the drug-induced changes in rivalry phase durations, subjects showed clear changes in psychological state as indexed by the 5D-ASC ( altered states of consciousness) rating scales. This study suggests the involvement of serotonergic pathways in binocular rivalry and supports the previously proposed role of a brainstem oscillator in perceptual rivalry alternations and symptoms of psychosis.

Detecting multipartite entanglement

We discuss the problem of determining whether the state of several quantum mechanical subsystems is entangled. As in previous work on two subsystems we introduce a procedure for checking separability that is based on finding state extensions with appropriate properties and may be implemented as a semidefinite program. The main result of this work is to show that there is a series of tests of this kind such that if a multiparty state is entangled this will eventually be detected by one of the tests. The procedure also provides a means of constructing entanglement witnesses that could in principle be measured in order to demonstrate that the state is entangled.

Fossil biotas from the Okanagan Highlands, southern British Columbia and northeastern Washington State: climates and ecosystems across an Eocene landscape

The late Early to early Middle Eocene Okanagan Highlands fossil sites, spanning -1000 km north-south (northeastern Washington State, southern British Columbia) provide an opportunity to reconstruct biotic communities across a broad upland landscape during the warmest part of the Cenozoic. Plant taxa from these fossil sites are characteristic of the modern eastern North American deciduous forest zone, principally the mixed mesophytic forest, but also include extinct taxa, taxa known only from eastern Asian mesothermal forests, and a small number of taxa restricted to the present-day North American west coast coniferous biome. In this preliminary report, paleoclimates and forest types are reconstructed using collections from Republic in Washington State, USA., and Princeton, Quilchena, Falkland, McAbee, Hat Creek, Horsefly, and Driftwood Canyon in British Columbia, Canada. Both leaf margin analysis (LMA) and quantitative bioclimatic analysis of identified nearest living relatives of megaflora indicated upper microthermal to lower mesothermal moist environments (MAT -10-15 degrees C, CMMT > 0 degrees C, MAP > 100 cm/year). Some taxa common to most sites suggest cool conditions (e.g., Abies, other Pinaceae; Alnus, other Betulaceae). However, all floras contain a substantive broadleaf deciduous element (e.g., Fagaceae, Juglandaceae) and conifers (e.g., Metasequoia) with the bioclimatic analysis yielding slightly higher MAT than LMA. Thermophilic (principally mesothermal) taxa include various insects, the aquatic fern Azolla, palms, the banana relative Ensete, taxodiaceous conifers, Eucommia and Gordonia, taxa which may have occurred near their climatic limits. The mixture of thermophilic and temperate insect and plant taxa indicates low-temperature seasonality (i.e., highly equable climate).

Continuous-variable quantum-state sharing via quantum disentanglement

Quantum-state sharing is a protocol where perfect reconstruction of quantum states is achieved with incomplete or partial information in a multipartite quantum network. Quantum-state sharing allows for secure communication in a quantum network where partial information is lost or acquired by malicious parties. This protocol utilizes entanglement for the secret-state distribution and a class of quantum disentangling protocols for the state reconstruction. We demonstrate a quantum-state sharing protocol in which a tripartite entangled state is used to encode and distribute a secret state to three players. Any two of these players can collaborate to reconstruct the secret state, while individual players obtain no information. We investigate a number of quantum disentangling processes and experimentally demonstrate quantum-state reconstruction using two of these protocols. We experimentally measure a fidelity, averaged over all reconstruction permutations, of F=0.73 +/- 0.02. A result achievable only by using quantum resources.

Better Bell-inequality violation by collective measurements

The standard Bell-inequality experiments test for violation of local realism by repeatedly making local measurements on individual copies of an entangled quantum state. Here we investigate the possibility of increasing the violation of a Bell inequality by making collective measurements. We show that the nonlocality of bipartite pure entangled states, quantified by their maximal violation of the Bell-Clauser-Horne inequality, can always be enhanced by collective measurements, even without communication between the parties. For mixed states we also show that collective measurements can increase the violation of Bell inequalities, although numerical evidence suggests that the phenomenon is not common as it is for pure states.

Bright entanglement and the Einstein-Podolsky-Rosen paradox with coupled parametric oscillators

We show that two evanescently coupled chi((2)) parametric oscillators provide a tunable bright source of quadrature squeezed light, Einstein-Podolsky-Rosen correlations and quantum entanglement. Analysing the system in the above threshold regime, we demonstrate that these properties can be controlled by adjusting the coupling strengths and the cavity detunings. As this can be implemented with integrated optics, it provides a possible route to rugged and stable EPR sources. (C) 2005 Elsevier B.V. All rights reserved.

Bright entanglement in the intracavity nonlinear coupler

We show that the intracavity Kerr nonlinear coupler is a potential source of bright continuous variable entangled light beams which are tunable and spatially separated. We use a linearized fluctuation analysis to calculate the necessary correlations in regimes where it is valid. This means that we are treating regimes where the system exhibits Gaussian statistics so that well-known criteria are both necessary and sufficient to demonstrate entanglement. This system may be realized with integrated optics and thus provides a potentially rugged and stable source of bright entangled beams.