Studies of Charge Exchange in a High‐Pressure Pulsed Electron Impact Source

This is the publisher's version, also available electronically from http://scitation.aip.org/content/aip/journal/jcp/56/3/10.1063/1.1677327.A high pressure pulsed ion source has been used in a time‐of‐flight mass spectrometer in order to study the charge exchangereactions in Ar–H2 and Ar–D2 systems using the ion source in the Čermák mode of operation. As the source was used in a pulsed mode, it was possible to identify the various secondary ions arising from the charge exchangereactions in these systems. Very good agreement has been shown to exist between the experimental results and simple theoretical deductions. Calculations have been made to determine the cross sections for the charge exchangereactions between the various species from the experimental data

An accurate description of quantum size effects in InP nanocrystallites over a wide range of sizes

We obtain an effective parametrization of the bulk electronic structure of InP within the Tight Binding scheme. Using these parameters, we calculate the electronic structure of InP clusters with the size ranging upto 7.5 nm. The calculated variations in the electronic structure as a function of the cluster size is found to be in excellent agreement with experimental results over the entire range of sizes, establishing the effectiveness and transferability of the obtained parameter strengths.Comment: 9 pages, 3 figures, pdf file available at http://sscu.iisc.ernet.in/~sampan/publications.htm

Synthesis of CdS and CdSe nanocrystallites using a novel single-molecule precursors approach

The synthesis of CdS and CdSe nanocrystallites using the thermolysis of several dithioor diselenocarbamato complexes of cadmium in trioctylphosphine oxide (TOPO) is reported. The nanodispersed materials obtained show quantum size effects in their optical spectra and exhibit near band-edge luminescence. The influence of experimental parameters on the properties of the nanocrystallites is discussed. HRTEM images of these materials show well-defined, crystalline nanosized particles. Standard size fractionation procedures can be performed in order to narrow the size dispersion of the samples. The TOPO-capped CdS and CdSe nanocrystallites and simple organic bridging ligands, such as 2,2¢-bipyrimidine, are used as the starting materials for the preparation of novel nanocomposites. The optical properties shown by these new nanocomposites are compared with those of the starting nanodispersed materials

Irradiation-induced Ag nanocluster nucleation in silicate glasses: analogy with photography

The synthesis of Ag nanoclusters in sodalime silicate glasses and silica was studied by optical absorption (OA) and electron spin resonance (ESR) experiments under both low (gamma-ray) and high (MeV ion) deposited energy density irradiation conditions. Both types of irradiation create electrons and holes whose density and thermal evolution - notably via their interaction with defects - are shown to determine the clustering and growth rates of Ag nanocrystals. We thus establish the influence of redox interactions of defects and silver (poly)ions. The mechanisms are similar to the latent image formation in photography: irradiation-induced photoelectrons are trapped within the glass matrix, notably on dissolved noble metal ions and defects, which are thus neutralized (reverse oxidation reactions are also shown to exist). Annealing promotes metal atom diffusion, which in turn leads to cluster nuclei formation. The cluster density depends not only on the irradiation fluence, but also - and primarily - on the density of deposited energy and the redox properties of the glass. Ion irradiation (i.e., large deposited energy density) is far more effective in cluster formation, despite its lower neutralization efficiency (from Ag+ to Ag0) as compared to gamma photon irradiation.Comment: 48 pages, 18 figures, revised version publ. in Phys. Rev. B, pdf fil

Logical Step-Indexed Logical Relations

Appel and McAllester's "step-indexed" logical relations have proven to be a simple and effective technique for reasoning about programs in languages with semantically interesting types, such as general recursive types and general reference types. However, proofs using step-indexed models typically involve tedious, error-prone, and proof-obscuring step-index arithmetic, so it is important to develop clean, high-level, equational proof principles that avoid mention of step indices. In this paper, we show how to reason about binary step-indexed logical relations in an abstract and elegant way. Specifically, we define a logic LSLR, which is inspired by Plotkin and Abadi's logic for parametricity, but also supports recursively defined relations by means of the modal "later" operator from Appel, Melli\`es, Richards, and Vouillon's "very modal model" paper. We encode in LSLR a logical relation for reasoning relationally about programs in call-by-value System F extended with general recursive types. Using this logical relation, we derive a set of useful rules with which we can prove contextual equivalence and approximation results without counting steps

Tuning the energetics and tailoring the optical properties of silver clusters confined in zeolites

The integration of metal atoms and clusters in well-defined dielectric cavities is a powerful strategy to impart new properties to them that depend on the size and geometry of the confined space as well as on metal-host electrostatic interactions. Here, we unravel the dependence of the electronic properties of metal clusters on space confinement by studying the ionization potential of silver clusters embedded in four different zeolite environments over a range of silver concentrations. Extensive characterization reveals a strong influence of silver loading and host environment on the cluster ionization potential, which is also correlated to the cluster's optical and structural properties. Through fine-tuning of the zeolite host environment, we demonstrate photoluminescence quantum yields approaching unity. This work extends our understanding of structure property relationships of small metal clusters and applies this understanding to develop highly photoluminescent materials with potential applications in optoelectronics and bioimaging

Role of Temperature in the Growth of Silver Nanoparticles Through a Synergetic Reduction Approach

This study presents the role of reaction temperature in the formation and growth of silver nanoparticles through a synergetic reduction approach using two or three reducing agents simultaneously. By this approach, the shape-/size-controlled silver nanoparticles (plates and spheres) can be generated under mild conditions. It was found that the reaction temperature could play a key role in particle growth and shape/size control, especially for silver nanoplates. These nanoplates could exhibit an intensive surface plasmon resonance in the wavelength range of 700–1,400 nm in the UV–vis spectrum depending upon their shapes and sizes, which make them useful for optical applications, such as optical probes, ionic sensing, and biochemical sensors. A detailed analysis conducted in this study clearly shows that the reaction temperature can greatly influence reaction rate, and hence the particle characteristics. The findings would be useful for optimization of experimental parameters for shape-controlled synthesis of other metallic nanoparticles (e.g., Au, Cu, Pt, and Pd) with desirable functional properties

Synthesis of Starch-Stabilized Ag Nanoparticles and Hg2+Recognition in Aqueous Media

The starch-stabilized Ag nanoparticles were successfully synthesized via a reduction approach and characterized with SPR UV/Vis spectroscopy, TEM, and HRTEM. By utilizing the redox reaction between Ag nanoparticles and Hg2+, and the resulted decrease in UV/Vis signal, we develop a colorimetric method for detection of Hg2+ion. A linear relationship stands between the absorbance intensity of the Ag nanoparticles and the concentration of Hg2+ion over the range from 10 ppb to 1 ppm at the absorption of 390 nm. The detection limit for Hg2+ions in homogeneous aqueous solutions is estimated to be ~5 ppb. This system shows excellent selectivity for Hg2+over other metal ions including Na+, K+, Ba2+, Mg2+, Ca2+, Fe3+, and Cd2+. The results shown herein have potential implications in the development of new colorimetric sensors for easy and selective detection and monitoring of mercuric ions in aqueous solutions