Energy Trapping in Dications

The energy interaction curves of a number of diatomic and polyatomic dication systems were calculated in order to study their energy-trapping properties. Generally, the ab initio complete active space multiconfiguration self-consistent field method was used in an extended valence + polarization basis set, with compact effective potentials replacing the core electrons. The diatomic dications include all ten possible binary combinations of oxygen, sulphur, selenium, and tellurium. O₂²⁺ shows the largest exothermicity, measured from equilibrium to the monocation combination asymptote, and highest barrier to dissociation. The calculated equilibrium bond length and harmonic vibrational frequency agree very well with experiment. The O₂²⁺, SO²⁺, SeO²⁺, and TeO²⁺ series show progressively decreasing exothermicities but similar barrier heights. The non-oxides, in contrast, show similar exothermicities but decreasing barriers with increasing size of the atom constituents. These trends are interpreted in terms of both valence bond curve-crossing and molecular orbital bonding models. The ozone dication, O₃²⁺, is found to have a number of low-lying singlet and triplet stationary state structures spanning near-linear to D_3h2+ symmetries. Although the calculated exothermicity is even larger than for O₂²⁺, the barrier to O₂⁺ + O⁺ dissociation is predicted to be low in each case. O₂²⁺ surrounded by six argon atoms to model an isolating environment shows increased equilibrium O–O bond length, decreased exothermicity, and increased barrier to dissociation, relative to the bare dication. O₂²⁺ flanked at each end by a perpendicularly oriented H₂ molecule in a staggered conformation is obstructed from direct conversion to the water dimer dication by a high barrier. However, [(H₂O)₂]²⁺ dissociates smoothly from equilibrium to two water monocations with a large exothermicity but a small barrier.     

Reasoning about Knowledge: A Response by the Authors

Minds and Machines -     

Signal set design with constrained amplitude spectrum and specifiedtime-bandwidth product

A new method for designing signals with a given time-bandwidth product, such that all the signals in the set have a flat amplitude spectrum and have low cross-correlation function values is introduced. It is shown that these signals lie on a signal parameter space ellipse. For a given duration and bandwidth, it is possible to trade off the cardinality of the set for better cross-correlation properties between remaining members of the set. Proof that the cross-correlation between these signals is bounded from above by a factor proportional to the square-root of inverse distance between these signals along one of the axes of the ellipse is given. It is also shown that the cross-correlation between two signals that are furthest apart is bounded by the square-root of inverse time-bandwidth product of the signals in the set. An example design is then given and a comparison of this signal set to some well-known signal sets illustrates that it performs better when the metric is maximum cross-correlation value. The proposed signal set also has the advantage that it can be designed for any time-bandwidth product instead of discrete values     

Highly Efficient Ge-Rich Ge<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Te Thermoelectric Alloys

The search for alternative energy sources is presently at the forefront of applied research. In this context, thermoelectricity for direct energy conversion from thermal to electrical energy plays an important role. This paper is concerned with the development of highly efficient p-type Ge _x Pb_1−x Te alloys for thermoelectric applications, using spark plasma sintering. The carrier concentration of GeTe was varied by alloying of PbTe and/or by Bi₂Te₃ doping. Very high ZT values up to ~1.8 at 500°C were obtained by doping Pb_0.13Ge_0.87Te with 3 mol% Bi₂Te₃.     

Population-based incremental interactive concept learning for image retrieval by stochastic string segmentations

We propose a method for concept-based medical image retrieval that is a superset of existing semantic-based image retrieval methods. We conceive of a concept as an incremental and interactive formalization of the user's conception of an object in an image. The premise is that such a concept is closely related to a user's specific preferences and subjectivity and, thus, allows to deal with the complexity and content-dependency of medical image content. We describe an object in terms of multiple continuous boundary features and represent an object concept by the stochastic characteristics of an object population. A population-based incrementally learning technique, in combination with relevance feedback, is then used for concept customization. The user determines the speed and direction of concept customization using a single parameter that defines the degree of exploration and exploitation of the search space. Images are retrieved from a database in a limited number of steps based upon the customized concept. To demonstrate our method we have performed concept-based image retrieval on a database of 292 digitized X-ray images of cervical vertebrae with a variety of abnormalities. The results show that our method produces precise and accurate results when doing a direct search. In an open-ended search our method efficiently and effectively explores the search space.     

Functional Free‐Standing Graphene Honeycomb Films

Fabricating free‐standing, three‐dimensional (3D) ordered porous graphene structure can service a wide range of functional materials such as environmentally friendly materials for antibacterial medical applications and efficient solar harvesting devices. A scalable solution processable strategy is developed to create such free‐standing hierarchical porous structures composed of functionalized graphene sheets via an “on water spreading” method. The free‐standing film shows a large area uniform honeycomb structure and can be transferred onto any substrate of interest. The graphene‐based free‐standing honeycomb films exhibit superior broad spectrum antibacterial activity as confirmed using green fluorescent protein labeled Pseudomonas aeruginosa PAO1 and Escherichia coli as model pathogens. Functional nanoparticles such as titanium dioxide (TiO₂) nanoparticles can be easily introduced into conductive graphene‐based scaffolds by premixing. The formed composite honeycomb film electrode shows a fast, stable, and completely reversible photocurrent response accompanying each switch‐on and switch‐off event. The graphene‐based honeycomb scaffold enhances the light‐harvesting efficiency and improves the photoelectric conversion behavior; the photocurrent of the composite film is about two times as high as that of the pure TiO₂ film electrode. Such composite porous films combining remarkably good electrochemical performance of graphene, a large electrode/electrolyte contact area, and excellent stability during the photo‐conversion process hold promise for further applications in water treatment and solar energy conversion.     

Nanometer‐Scale Mapping of Elastic Modules in Biogenic Composites: The Nacre of Mollusk Shells

In this study, a newly developed nanoscale modulus mapping is applied in order to visualize the 2D‐distribution of mechanical characteristics in the aragonitic nacre layer of Perna canaliculus (green mussel) shells. Modulus maps provide lateral resolution of about 10 nm. They allow the aragonitic mineral (CaCO₃) tablets and the interfaces between them to be clearly resolved, which are filled by an organic substance (mainly beta‐chitin). The experimental data are compared with finite element simulations that also take into account the tip radius of curvature and the thickness of organic layers, as measured by means of scanning electron microscopy with back‐scattered electrons. Based on this comparison, the Young modulus of beta‐chitin is extracted. The obtained number, E_β = 40 GPa, is higher than previously evaluated. The collected maps reveal that the elastic modules in the nacre layer change gradually across the ceramic/organic interfaces within a spatial range four times wider than the thickness of the organic layers. This is possibly due to inhomogeneous distribution of organic macromolecules within ceramic tablets. According to the data, the concentration of macromolecules gradually increases when approaching the organic/ceramic interfaces. A behavior of this type is unique to biogenic materials and distinguishes them from synthetic composite materials. Finally, three possible mechanisms that attempt to explain why gradual changes of elastic modules significantly enhance the overall resistance to fracture of the nacre layer are briefly discussed. The experimental findings support the idea that individual ceramic tablets, comprising the nacre, are built of the compositionally and functionally graded ceramic material. This sheds additional light on the origin of the superior mechanical properties of biogenic composites.     

Structural Evolution Following Spinodal Decomposition of the Pseudoternary Compound (Pb0.3Sn0.1Ge0.6)Te

Pseudoternary (Ge,Sn,Pb)Te compounds display favorable thermoelectric properties. Spinodal decomposition in the quasiternary (Ge,Sn,Pb)Te system is at the origin of a wide solubility gap at low Sn concentrations. The structural evolution of the spinodal decomposition was investigated as a function of aging time at 500°C, using x-ray diffraction, electron microscopy, and scanning electron microscopy. The evolution of the structure at 500°C consists initially of a short diffusion-controlled demixing stage into Pb- and Ge-rich coherent areas, with compositions corresponding to the inflection points of the free-energy curve. The Pb-rich areas adopt configurations associated with the directions of the soft elastic moduli of the cubic compound. Both the Pb- and Ge-rich areas are supersaturated and undergo in a second stage a nucleation and growth process and give rise to a biphased structure with equilibrium compositions corresponding to the boundaries of the miscibility gap. The resulting Pb-rich areas display a relatively stable microstructure suggesting the presence of long-range interactions between the Pb-rich precipitates in the Ge-rich matrix.     

Frequency-Dependent Attenuation Effects in Pulsed Doppler Ultrasound: Experimental Results

The quantitative capability of pulsed Doppler ultrasound in clinical practice is limited by the effects of frequency-dependent attenuation of ultrasound in tissue, as well as several other spectral-broadening mechanisms which distort the Doppler spectrum of an ultrasonic echo. In this communication, we present results of in vitro experiments which demonstrate the magnitude of the errors expected in clinical measurements of blood flow parameters when frequency-dependent attenuation Of ultrasound in biological tissue is ignored. It is shown that errors as large as 15 percent may occur in Doppler measurements of blood flow velocity through 7 cm of intervening tissue. A comparison is also made between experimental results and a theoretical model which includes the effects of scattering and attenuation.